Calcia catalyzed resins

ABSTRACT

This specification discloses ecologically desirable, improved binder compositions suitable for bonding fibers. These binders exhibit low pollutant characteristics and improved properties, due to a combination into the binder of aminoplast resins or non phenolic monomeric materials capable of co-condensing with formaldehyde, together with a substantially phenol free, low mono methylolphenol high .[.ortho para di.]. .Iadd.2,4,6-tri .Iaddend.methylol .[.phenol.]. .Iadd.phenols .Iaddend.content, water soluble thermosetting phenol formaldehyde resole solution. The phenolic resole resin is made to conform to the desired composition by mixing together a high mole ratio of formaldehyde with phenol and calcium hydroxide with cooling so that very little reaction takes place. The reaction is then allowed to proceed according to a carefully controlled temperature-time cycle without external heat input until substantially all the phenol has reacted to form condensation products and yet the mixture is still infinitely dilutable with water. Such binder compositions may be applied at solids levels of 1% to 80% and contain much lower phenolic resin component than binders of prior art with similar bonding characteristics.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a continuation-in-part of both (1) application Ser.No. 400,145, filed Sept. 24, 1973, now abandoned, which was acontinuation of application Ser. No. 226,265, filed Feb. 14, 1972, nowabandoned, which was a continuation-in-part of application Ser. No.44,616, filed June 8, 1970, now abandoned; and (2) application Ser. No.226,234, filed Feb. 14, 1972, now abandoned, which was acontinuation-in-part of application Ser. No. 44,616, filed June 8, 1970,now abandoned.

This invention relates to the preparation of substantially phenol-freewater soluble thermosettable phenol formaldehyde resol solutions, to thepreparation of binder compositions therefrom and to fibre articles suchas glassfibre insulating products so bonded.

Phenol formaldehyde resole resins are well known in the art. There alsoexists prior art pertaining to the preparation and use of these andother resins, monomers and other additives in binder compositions forthe bonding of the fibre products. Binder systems from such resoles, forexample for glass fibres, usually comprise, in addition, alsosubstantial percentages of co-condensable monomers and polymers, e.g.urea, and urea formaldehyde resins and the more costly dicyandiamide andmelamine formaldehyde resins, along with other ingredients such asmineral oil, emulsifiers and stabilizers. Such binders are applied toglass fibres at high temperatures, as dilute aqueous dispersions orsolutions. Similar compositions are used for bonding differentmaterials, such as wood fibre or chip products, plywood and paperlaminates. Those skilled in the arts are making continuing great effortsto optimize resole resins for use in bonding compositions.

For use in binders for glass fibres, prior art resins suffer from somecombination of the following properties which limit their usefulness forthis end use:

The solubility in water (considered in terms of dilutability) or inother binder ingredients may be limited and lead to blockage of lines,filters, and spray nozzles, etc.

The stability in storage before conversion into a binder is inadequate.

The resin may contain excessive unreacted phenol which is steam volatileand escapes to the atmosphere during binder applications to the fibersand necessitating expensive pollution control equipment to eliminate itand to dispose of the waste.

The resin contains volatile phenol alcohols (mono methylol phenols)which can escape to atmosphere during application, forming stableaerosols which are difficult to eliminate and necessitate furtherpollution control equipment to eliminate them and to dispose of thewastes.

The cured bonding material may contain water soluble alkali metal saltsderived from the catalyst used to promote the methylolation reaction.Such alkali metal salts are detrimental to bond strength retention andpromote corrosion where glass fibre products are used in contact withcommon metals.

The cost of the phenol formaldehyde resin produced may be excessive dueto composition, catalyst cost and low resinification efficiency, i.e.:low yield of organic resin solids per unit volume charged or per unit ofreactor time and volume.

The ratio of resin or binder solids which is retained in the finishedproduct to those applied (application efficiency) is inadequate.Application efficiency is related to and simulated by the volatilitytest known as "Cone Efficiency".

The resistance of the cured binder to glass bond under conditions ofhigh moisture and/or high temperature is inadequate.

The phenol formaldehyde resol may not be fully compatible with otherdesirable binder components.

The resoles and binder compositions of the present invention exhibit anadvantageous balance of properties based on the above criteria and offermaterial advantages over prior art resins. These advantages have beendemonstrated convincingly by large scale industrial use of saidsubstantially phenol free, high mole ratio, calcium catalysed phenolformaldehyde resoles in binders for glass fibers. It is expected saidresoles would perform satisfactorily in binders for laminated paper andwood products and the like with similar advantages.

Said advantages are principally:

a. An ecologically desirable reduction in atmospheric pollution duringcuring due to the very low phenol and monomethylolphenol content of theresole resin. These two toxic substances are steam volatile and escapeto the atmosphere during the manufacturing process and elimination ofsuch pollution is a great benefit.

b. A further reduction in pollution due to using a lesser proportion ofphenolic resole in the bonding solids. This is possible because the highmole ratio permits an increase in non phenolic film forming materials.

c. A further reduction in pollution due to higher yields of cured resinsolids from the applied binder.

d. An improvement in the case of control of the resole manufacturingprocess, particularly significant in relation to continuous productiontechniques.

e. An improvement in the stability of the resole and binders made fromit.

Discussion of the Prior Art

The extensive prior art on water soluble phenolic resoles does notdisclose any process to give these benefits.

Consider the vary low phenol and low monomethyol phenol obtained by thisprocess. In U.S. Pat. No. 2,940,954, June 14, 1960, Barr et al haveworked on this probelm and disclose a process for obtaining low valuesby solvent extraction. They indicate that a resole made with a moleratio of 3 moles formaldehyde to 1 mole phenol combined with an alkalinecatalyst by the recognised methods known to those skilled in the artwould analyse to show 3% unreacted phenol and 10% or moremonomethylolphenol at the end of the reaction (column 3, lines 28 to64).

In Canadian Pat. No. 658,438, Feb. 26, 1973, Smucker disclose reactionof phenol with formaldehyde and barium hydroxide catalyst untilsubstantially all the phenol is reacted. However, such a mixture is notstable unless the resole is immediately converted to a terpolymer resinbased on phenol formaldehyde, urea, dicyandiamide, and melamine and theresole itself cannot be obtained phenol free for use in bindercompositions. Even when converted to a terpolymer the resins of theSmucker process do not show the stability of resins of this invention.

High mole ratio resins are disclosed in a number of prior art patents.For instance Gladney and Deuzeman U.S. Pat. No. 3,624,274 Nov. 30, 1971,shows resins with mole ratios of 1.9 to 2.8 mols formaldehyde per moleof phenol. (1.9-2.8:1). Whetstone U.S. Pat. No. 2,441,860, May 18, 1948shows mole ratios from 1.0:1 to 4.0:1. Higashi U.S. Pat. No. 2,862,910Dec. 2, 1958 shows mole ratios 0.8:1 to 3.0:1. LeBlanc U.S. Pat. No.3,304,345, shows ratios 1.0:1 to 4.0:1 Monsanto Pat. U.K. Pat. No.1,023,881, Lambuth shows mole ratios 2.2:1 to 3.5:1. Monsanto Pat. U.K.Pat. No. 733,568 shows mole ratios 2.25:1 to 3.33:1.

The use of phenolic resoles as sole binding agent for glass fibres isrestricted effectively to resoles with a formaldehyde to phenol moleratio of 2.6:1. Resoles with higher mole ratios do not develope adequatebond strength, and have therefore not been used in glass bindercomposition. It was a surprising and novel discovery to find that theaddition of other co-condensable materials such as urea, dicyandiamideand the like to these high mole ratio resins in the range 2.8:1 to 4.5:1and especially 3.2:1 to 4.4:1 mols formaldehyde per mol phenol restoredthe bond strength to an acceptable level, and that good quality glassbinders can be produced based on such high mole ratio resins.

The use of calcium as a catalyst is described in the art as examplifiedby Gladney U.S. Pat. No. 3,624,247, LeBlanc U.S. Pat. No. 3,304,345,Monsanto U.K. Pat. No. 1,023,881, and Monsanto U.K. Pat. No. 733,568.Alkaline earths are described as catalyst in patents such as WhetstoneU.S. Pat. No. 2,441,860 and Smucker Canadian Pat. No. 658,438. All thesepatents make a general assumption that one alkaline catalyst isequivalent to another and indeed interchangeable for resole productionand that the reaction rate and resulting composition depend on thehydroxyl concentration (based on the phenol present).

A detailed study of the catalysis of mixtures of phenol and formaldehydeby calcium hydroxide has shown that this assumption is incorrect. Thereare considerable differences in composition depending on the specificcatalyst used, and also on the mole ratio of formaldehyde to phenol.

It is found that use of calcium as a catalyst results in:

a. Preferential conversion of more formaldehyde to organic resin solids,which increases resinification efficiency.

b. Formation of a higher quantity of .[.O,P-dimethylol phenol which is adesired product.]. .Iadd.2,4,6-trimethylol phenols which are desiredproducts. .Iaddend.

c. An increase in yield as shown by cone efficiency tests.

d. A reduction in the content of monomethylol phenol, .Iadd.and.Iaddend.diphenyls .[.and trimethylol phenol.]..

The properties of the resole catalysed by calcium are modified as aresult of this change in composition so that it is feasible to allow thecondensation to proceed until no free phenol is detectable and yet theresole is still infinitely dilutable with water and remains so for asufficiently long period to allow cooling to about 70° F. and still beinfinitely dilutable. This behaviour due to the use of calcium is noveland unexpected and not disclosed in or deducible from the prior art.

To take advantage of the ability to react to such low phenol andmonomethylol phenol as a practical day to day process demands a highdegree of uniformity of operation in manufacture.

The patents mentioned above in discussion of prior art with regard tomole ratio and catalyst all call for heating to promote the reaction. Itis a particularly novel feature of this invention that the conditionsspecified mean that it it not necessary to supply heat from an externalsource to bring about reaction. Using these high mole ratios offormaldehyde to phenol and calcium oxide or hydroxide as a catalyst withthe water content restricted to no more than 6-10 moles per mole ofreactants it is found that the reaction can be controlled by coolingonly.

Against this general background of modern resin, binder and glass fibretechnology, of the environmental control requirements and of theconstraints inherent in the art of preparing water solublethermosettable resin compositions for the bonding of glass fibres, somemajor objectives of this invention are set out herein:

a. To reduce the emission of phenolic or other organic pollutants to theatmosphere by reducing the content of volatile compounds which becomepollutants, per unit of aqueous thermosettable phenol formaldehyderesol.

b. Further reduce pollution by reducing the proportions of phenolicresol used in binder compositions for bonding glass.

c. To retain infinite dilutability of the resol with distilled water, byminimizing the formation of water insoluble condensation products, suchas for instance higher phenyls.

d. To react all available phenol (B.P.=181° C.) in the condensationreaction and minimize the formation of o-monomethylol phenol(=α,2-dihydroxy toluene or Saligenin; which sublimates at 100° C.); andp- mono-methyl phenol (=α,4-dihydroxy toluene, B.P.=252° C.); which arevolatile per se or in the presence of steam.

e. To prepare such aqueous phenolic resins in batch type or continuousoperation, requiring no after treatment for reduction of the volatilesby secondary treatment, e.g. by distillation or solvent extraction.

f. To retain a moisture resistant non-corrosive bond between glass fibreand heat cured binder.

g. To minimize the amount and settling characteristics of any insolubleproduct of catalyst neutralization.

h. It was a major objective of the work leading to this invention tointroduce the catalyst in suitable proportions so as to create a highenough exotherm to carry the reaction to completion without input ofexternal heat, controlling temperatures throughout the cycle by coolingonly. The purpose is twofold. In industrial reaction vessels it has beenobserved that advanced, water insoluble condensation products are formedon batch-type heating surfaces (coils, jackets), and at least in partare released into the resin cook. Secondly, it is very desirable foreffective reaction control in a continuous process for the manufactureof water soluble, aqueous phenol formaldehyde resins of the type heredescribed, that temperature control be restricted to the cooling mode.

i. To dissolve all catalysts without residue.

j. To produce a material in which any resulting insoluble neutralizationproducts of alkaline earth metal catalysts are substantially non-settingand non-agglomerating, and have little or no tendency to block pipelines.

k. To reduce the content of soluble alkali metal salts, and particularlyalkali metal chlorides, so they contribute not more than 1.8% of R₂ O(R=Na, K or other alkali metal) to the binder composition.

l. To obtain a moisture resistant non-corrosive bond to glass fibres.This precludes the use of such phenolic resins derived from catalyzationwith high concentrations of hydroxides or salts of alkali metals, as aredisclosed in British Pat. No. 1,023,881 Monsanto, published Mar. 30,1966.

The data from our experimentation undertaken to meet or to approach theabove objectives and constraints suggested that for the preparation ofco-condensable thermosetting bonding materials from phenol formaldehyde,amine type monomers and/or amine formaldehyde condensation products, thephenol formaldehyde resole component might tolerate a relatively highpercentage of unreacted formaldehyde. Thus it could be prepared fromusually high formaldehyde mole ratio charges, even though the prior artindicates clearly that detrimental effects of such high mole ratios uponthe aging and weathering properties of the cured phenolic resin per seare to be expected.

In the art of making binders for bonding glass fibres the use ofpreviously known phenolic resins as sole binder material was restrictedeffectively to resoles with a formaldehyde to phenol mole ratio of2.6:1. An increase of mole ratio results in a decrease in bond strengthand at ratios of 3:1 the product is not a suitable bonding agent. It wastherefore surprising and unexpected to find that high mole ratio resinsin the range of 2.8 to 4.5 or especially 3.2 to 4.4 do form good bindersin combination with other co-condensable monomers and polymers such asurea, dicyandiamide, urea formaldehyde resins, melamine formaldehyderesins, and other binder ingredients such as mineral oil, emulsifiersand stabilizers.

It appeared further advantageous to investigate high catalystconcentrations. The prior art teaches that inorganic alkaline catalystsfor the condensation reaction of phenol with formaldehyde can beselected interchangeably from alkaline earth metal and .[.alkaline.]..Iadd.alkali .Iaddend.metal hydroxides, oxides and salts of acids ofdissociation constant not greater than 1.1×10⁻². In view of theobjectives enumerated above it was taken into consideration that:

a. In the case of soda (Na₂ O) or potassia (K₂ O) catalyzed resins,neutralization with acids (hydrochloric, sulfuric or carbonic) formssoluble salts in the aqueous solution in quantities objectionable forthe use of such resins, e.g. for bonding glass fibres. The need arisesto de-ionize such resins by ion-exchange methods.

b. In the case of the use of barium hydroxide as catalyst, limitationsare encountered in solubility, cost, and the properties of theneutralization product. Barium sulphate having a specific gravity of 4.5must be precipitated ultra-fine in order to avoid settling duringstorage, or blockage of lines, filters, etc. Similarly, barium carbonatehas a gravity of 4.3.

On the other hand, calcium sulphate and calcium carbonate have specificgravities of 2.9 and 2.8 respectively. These calcium salts resistsettling in particle sizes as large as 1 to 2 microns, although they canbe readily obtained in sub-micron size particles. Calcium oxide andhydroxide were found to be superior to the other catalysts. It isconveniently used in powdered form, but calcium hydroxide solutions canalso be used subject to limitations in total water content of thereactants.

Within the parameters chosen by us and more closely spelled out below,we have found the following unexpected effects of catalyzation of thephenol formaldehyde reaction with calcium oxide or calcium hydroxide ascompared to prior art resins, and as compared to high mole ratio resinscatalyzed with comparable concentrations of sodium hydroxide or bariumhydroxide:

preferential conversion of more formaldehyde to organic resin solids,thus increased resinification efficiency.

preferential formation of .[.o-p-dimethylol phenol.]..Iadd.2,4,6-trimethylol phenols .Iaddend.increased cone efficiency

reduction in mono-methylol phenol content

reduced formation of diphenyls .[.and of tri-methylol phenol.].

increased chemical stability and shelf life

increased bond strength to glass fibres, when combined with urea, orother amine monomers, or with amino plast resins, in binder compositionsas described below.

The present invention therefore provides a method for making aninfinitely dilutable low phenol aqueous solution of thermosettablephenol formaldehyde resin, by selectively catalyzing and controlling themethylolation of phenol with formaldehyde to increase resinification,minimize the content of monomethylol phenols and higher phenyls andmaximize the content of .[.o-p-dimethylol phenols.]..Iadd.2,4,6-trimethylol phenols.Iaddend., thus producing a resinsolution component for binder formulations having low air and washwater-polluting characteristics when applied to a substrate, comprisingthe steps of (a) mixing U.S.P. phenol, in the absence of other monomers,with aqueous formaldehyde, in an amount of 2.8 to 4.5 of moles offormaldehyde per mol of phenol, and correspondingly up to about 10 molesof water per mol of the reactants, at a temperature not exceeding about85° F., and (b) introducing calcium oxide or calcium hydroxide catalyst,with cooling in an amount of 3.5 to 7 percent as calcium (Ca) based uponthe weight of phenol, (0.08 mol to 0.16 mol calcium (Ca) per mol ofphenol), (c) controlling the exothermic rise in the temperature of thereactants without heat input so as to increase to not more than about125° F. during at least the first hour of reaction, (d) continuing themethylolation reaction without heat input at a suitable temperature upto 155° F., and (e) terminating said reaction by cooling when thecondensation reaction product is substantially phenol-free, and is stillwater soluble.

In a further embodiment such a method for making infinitely dilutablesubstantially phenol free aqueous solutions of thermosettable phenolformaldehyde resins, by selectively catalyzing and controlling themethylolation of phenol with formaldehyde to increase resinification,minimize the content of monomethylol phenols and higher phenyls andmaximize the content of .[.o-p-dimethylol phenols.]..Iadd.2,4,6-trimethylol phenols.Iaddend., thus producing a resinsolution component for binder formulations having low air and wash waterpolluting characteristics when applied to a substrate, comprising thesteps of (a) mixing U.S.P. phenol, in the absence of other monomers,with aqueous formaldehyde in an amount of 3.2 to 4.4 moles offormaldehyde per mol of phenol, and correspondingly from 6 to 10 molesof water per mol of the reactants, at a temperature not exceeding about85° F., and, (b) introducing calcium oxide or calcium hydroxide catalystwith cooling up to or near its solubility limit in the aqueous mixturepresent, catalyst in an amount of 3.5 to 7 percent as calcium (Ca) basedupon the weight of phenol, (0.08 mol to 0.16 mol calcium (Ca) per mol ofphenol), (c) controlling the exothermic rise in temperature of thereactants without heat input so as to increase to not more than about125° F. during at least the first hour of reaction, (d) continuing themethylolation reaction without heat input at a suitable temperature upto 155° F., and (e) terminating said reaction by cooling when thecondensation reaction product is substantially phenol free, and is stillwater soluble.

The present invention further provides an aqueous solution of aninfinitely dilutable thermosettable phenol formaldehyde condensationresin, said resin characterized as follows: (i) not over about 0.5%unreacted phenol by weight, (ii) between 3 to 16% unreactedformaldehyde, by weight, (iii) between 2.3 to 2.7 methylol groups perphenol molecule, (iv) low content of water insoluble higher phenyls, (v)low content of monomethylolphenol, said solution being prepared byselectively catalyzing and controlling the methylolation of 1 mol ofphenol with 3.2 to 4.4 mols of formaldehyde with calcium oxide and nomore than 10 mols of water per mol of reactant, to suppress theformation of monomethylol phenols and higher phenyls, and to favour theformation .[.o-p-dimethylol phenol.]. .Iadd.2,4,6-trimethylolphenols.Iaddend..

The temperature is preferably maintained not higher than about 85° F. instep (a). The process may be batch or continuous, and there are severaladvantages in using this process in a continuous manner.

The phenol is introduced in the form of U.S.P. phenol .Iadd.("USP"denotes United States pharmacopoeia grade).Iaddend., in the absence ofmonomers such as other (substituted) phenols as may be found in naturalphenol, or such as amines, e.g. ureas, dicyandiamide, melamine, all ofwhich can react competitively with the formaldehyde present, leadinguncontrollably to indeterminate insoluble reaction products or to thierprecursors.

The formaldehyde is introduced in aqueous solution of 44% or moreconcentration, (containing no more methanol than 1% for stabilization).The formaldehyde is introduced in an amount of 2.8 to 4.5 or preferably3.2 to 4.4 moles per mole of phenol. Most preferably it may beintroduced in an amount of 3.5 to 4.0 mole per mole of phenol, andparticularly in an amount of about 3.6 to 3.8 moles per mole of phenol.Water may be added to the reactants if the formaldehyde solutionconcentration exceeds 44%, to adjust the ratio of from 6 to 10 moles ofwater per mol of the reactants and preferably 6.5 to 10. This water maybe added in the form of an aqueous solution of calcium hydroxidecatalyst. If too little water is present heat evolution on catalystaddition may be excessive, and the selectivity of the substitutionreaction suffers. Excess water will slow the reaction time down and mayadversely affect the terminal composition.

The reactants, phenol and formaldehyde which are normally commerciallystored at 140° F. and 120° F. respectively, are blended, while coolingto a temperature of no more than about 28° F., before addition ofcatalyst.

The catalyst addition is made under vigorous agitation and with coolingand at such a rate as to prevent premature condensation. Preferably thetemperature is held no higher than about 85° F. until all the alkalinecatalyst is added. The cooling may be reduced to let the temperaturerise without the use of an external heating source at such a rate thatthe temperature is no more than 125° F. after one hour. Calcium oxide ispreferred over calcium hydroxide catalyst when the reactor design hasadequate cooling capacity to handle it successfully.

The calcium catalyst is added as CaO or as Ca(OH)₂. It is generallyintroduced in an amount approximating its solubility in the system. Thiswill correspond to about 3.5 to 7 weight percent calcium based upon theweight of phenol, (0.08 to 0.16 mol .[.Ca(OH)₂ .]. .Iadd.Ca .Iaddend.permol of phenol), preferably to 4.9 to 5.9 weight percent, (0.11 to 0.14mol .Iadd.Ca .Iaddend.per mol of phenol) and most preferably to 5.1 to5.5% by weight of phenol (0.12 to 0.13 mol .Iadd.Ca .Iaddend.per mol ofphenol). The amount soluble will depend on the amount of water in thesystem.

The reaction may be carried out at any suitable temperature up to andpreferably no higher than about 155° F. and usually for a period of 3 to10 hours. Higher temperatures encourage excessive co-condensation andthe formation of insoluble products. The temperature is preferably to bereached from a charge temperature of not over about 85° F., eitherlinearily or in a stepwise increase whereby a first temperature nohigher than 125° F. is maintained for at least approximately one hour.The condensation reaction is arrested by cooling to 100° F. orpreferably to 70° F. either when the minimum content of free (unreacted)formaldehyde is attained or when minimum acceptable water dilutabilityis observed whichever may occur first. The minimum free formaldehydevalues are related to the starting ratio of formaldehyde to phenol.Accordingly, they can range from approximately 4.5 weight percentattained with a mole ratio of 2.8:1 to approximately 14.0% for a moleratio of 4.5:1 depending on the reaction temperatures and the operatingcharacteristics of the reaction equipment.

It has been observed, that in calcium catalyzed resins as describedhere, presumably because of their low content of insolubles andinsolubles precursors, the minimum constant free formaldehyde contentcan be attained safely before an unacceptable drop in dilutabilityoccurs. It has been further observed that in contrast particularly toprior art sodium hydroxide catalyzed resins, the calcium catalyzedresins are less prone to proceed to insolubility if the reaction iscontinued (such as up to as much as half an hour) beyond the usualcut-off point. This observation is in keeping with the unusual storagestability of these resins.

Calcium catalyzed resins of this invention can but need not beneutralized for storage and subsequent use as binder ingredients.Binders based on the non neutralized resins have been testedsuccessfully for large scale use. The neutralization of the catalystwith carbon dioxide gas, or alternate acids or acidic salts, is readilyand preferably conducted in such a fashion that a micron or submicronsize is formed which is non-settling, non-blocking in the resolsolutions and in the binder compositions made therefrom.

EXAMPLES

The following examples are intended to exemplify the principlesunderlying the present invention and are not intended to be limiting intheir scope.

The neutralized phenol formaldehyde resins produced in examples No. I toVII were sampled and several characteristics of these samples weretested, following test methods described further below.

The phenolic resins produced in these examples were then combined withother ingredients as disclosed further below to prepare aqueous thermosetting binders for bonding glass fibres. .Iadd.All percentagesmentioned in the following examples are by weight.

EXAMPLE I

Laboratory preparation of a calcium oxide catalyzed resin of a

Charge Ratio: 2.8 MOL Formaldehyde per 1.0 Mol Phenol

Ingredients

    ______________________________________                                        Formaldehyde -                                                                            aqueous - 44% solution                                                                         1995 gms                                         Phenol -    USP 98%          1005 gms                                         Calcium Oxide -                                                                           Ashgrove Springfield                                                                           50.7 gms                                                     high calcium pebble                                                                            (3.5% Ca)                                                    quicklime CaO 96.3%                                                                            (based on                                                    ground to (-10) mesh                                                                           weight of                                                    on U.S. standard scale                                                                         phenol)                                          ______________________________________                                    

Procedure

The formaldehyde was placed in a 3 liter glass reactor. The agitator wasstarted, phenol was added, and then calcium oxide was added. Thetemperature was allowed to rise to 125° F. in a period of about 1 hour.The temperature was held at 125° F. for 30 minutes. The temperature wasallowed to increase to 150° F. in 30 minutes. The temperature was heldat 150° F. until the free formaldehyde was reduced to 4.5% and thencooled to 75° F. The pH at the end of reaction was 8.70.

The resin was neutralized with carbon dioxide gas to a pH of 7.3 andsampled for tests.

Results

The properties and composition of the resin are shown in Table I,Example I.

EXAMPLE II

Industrial production of a calcium oxide catalyzed resin suitable foruse in binders particularly, in varying combinations with urea.

Charge Ratio: 2.8 Mol Formaldehyde per 1.0 Mol Phenol

Batch Size: 2000 gals.

Ingredients

    ______________________________________                                        Formaldehyde -                                                                           aqueous - 44% solution                                                                         1375 Imp. gals.                                   Phenol -   USP 98%           743 Imp. gals.                                   Calcium oxide -                                                                          Beachville rotary                                                                               406 lbs.                                                    crushed high calcium                                                          quicklime - CaO 92%-                                                          (-3) mesh on U.S.                                                             standard scale                                                     ______________________________________                                    

Procedure

The 3000 gals. reactor was charged with formaldehyde and phenol. Theagitator was started. The catalyst (calcium oxide) was added over aperiod of 15 minutes. When all the catalyst was charged, the temperaturewas allowed to rise to 125° F. in 1 hour. The temperature was held at125° F. for 1 hour. The temperature was allowed to increase to 150° F.over a period of 25 minutes, then held at 150° F. for about 11/4 hoursto a free formaldehyde content of 4.5%. The mixture was cooled to 80° F.The pH at the end of reaction was 8.4.

the resin was neutralized with carbon dioxide gas to a pH of 7.23, thensampled for tests.

Results

Properties and Composition--see Table I, Example II

EXAMPLE III

Laboratory preparation of a calcium oxide catalyzed resin of a

Charge Ratio: 3.1 Mol Formaldehyde per 1.0 Mol Phenol

Ingredients

    ______________________________________                                        Formaldehyde -                                                                            aqueous - 44%    2030 gms                                         Phenol -    USP 98%           920 gms                                         Calcium oxide -                                                                           Beachville rotary                                                                              53.9 gms                                                     crushed high calcium                                                                           (4% Ca)                                                      quicklime - CaO 93.5%                                                                          (based on                                        (-3) mesh on U.S.                                                                         weight of                                                                     standard scale   phenol)                                          ______________________________________                                    

Procedure

Formaldehyde was poured into the glass reactor, and the agitator wasstarted. The phenol was added, followed by the calcium oxide. Thetemperature was allowed to rise to 120° F. in a period of about 30minutes. The temperature was held at 120° F. for a period of 3 hours.The temperature was allowed to rise to 140° F. in 48 minutes then heldat 140° F. for 43 minutes. The temperature was then allowed to rise to150° F. and the mixture cooked at this temperature to a freeformaldehyde content of 5.5%. Then it was cooled to 75° F. The pH at theend of reaction was 7.9.

The resin was neutralized with carbon dioxide to a pH of 7.2, thensampled for tests.

Results

Properties and Composition--see Table I, Example III.

EXAMPLE IV

Laboratory preparation of a Calcium Oxide catalyzed resin of a

Charge Ratio: 3.5 Mol Formaldehyde per 1.0 Mol Phenol

Ingredients

    ______________________________________                                        Formaldehyde -                                                                            aqueous - 44% solution                                                                         2139.3 gms                                       Phenol -    USP 98%           860.7 gms                                       Calcium oxide -                                                                           Ashgrove Springfield                                                                            49.06 .Iadd.gms.Iaddend.                                    high calcium pebble                                                                            (4% Ca)                                                      quicklime - CaO 96.3%                                                                          (based on                                                    ground to (-10) mesh                                                                           weight of                                                    on U.S. standard phenol)                                          ______________________________________                                    

Procedure

The formaldehyde was poured into the glass reactor. The agitator wasstarted. Phenol was added, followed by calcium oxide. The temperaturewas allowed to rise to 100° F. and the mixture held at that temperaturefor 45 minutes. The temperature was allowed to increase to 110° F. in 30minutes period, and held at that temperature for 1 hour and 30 minutes.The temperature was allowed to rise to 130° F. in 30 minutes, and heldfor 1 hour. The temperature was allowed to rise to 150° F. and held atthat temperature till a free formaldehyde of 8.60%. The mixture wascooled to 75° F. The pH at the end of reaction was 8.3.

The resin was neutralized with carbon dioxide to a pH of about 7.2, thensampled for tests.

Results

Properties and Composition--see Table I, Example IV.

EXAMPLE V

Industrial production of a calcia catalyzed resin suitable for use inbinders particularly, in varying combinations with urea.

Charge Ratio: 3.7 Mol Formaldehyde per 1 Mol Phenol

Batch Size: 3000 gals.

Ingredients

    ______________________________________                                        Formaldehyde -                                                                            aqueous (44%) solution                                                                          2235 gals.                                      Phenol -    USP 98%            912 gals.                                      Ca(OH).sub.2 -                                                                            Beachville Chemical High                                                                         880 lbs.                                                   Calcium .[.Hydrate.]..Iadd.Hydroxide .Iaddend.Powder                          taken as 99% pure                                                 ______________________________________                                    

Procedure

The 3,000 gals. reactor was loaded with formaldehyde and phenol. Theagitator was started. The catalyst (Ca(OH)₂) was poured in over a periodof about one hour and 35 minutes.

The temperature at this point was about 86° F. It was held at 86° F. forabout 25 minutes, then the temperature was allowed to rise to 110° F.for about 28 minutes. The temperature was allowed to rise to 125° F. in20 minutes and held at 125° F. for about 40 minutes. The temperature wasallowed to rise to 150° F. in 50 minutes and held at 150° F. for about55 minutes to a free formaldehyde of 8.20%. The mixture was cooled to80° F. The final pH was 8.55.

The resin was neutralized with carbon dioxide to a pH of 7.8, thensampled for tests.

Results

Properties and composition--see Table I, Example V Also Freephenol--0.3% (by gas chromatography).

In addition the following proportions were determined by gaschromatography of the silylised resin:

Phenol--3.9

.[.o-methylol phenol--6.3.].

.[.p-methylol phenol--4.4.].

.[.di-phenyl-(o-subst)--11.1.].

.[.o-o-di-methylol phenol--0.6.].

.[.o-p-di-methylol phenol--52.7.].

.[.o-o-p-tri-methylol phenol--4.6.].

.[.di-phenyl (4 subst)--16.4.]..Iadd.

2 methylol phenol--6.3

4 methylol phenol--4.4

2,4-dimethylol phenol--11.1

2,4-dimethylol phenol monohemiformal--0.6

2,4,6-trimethylol phenols--57.3

tetra-substituted diphenyls--16.4 .Iaddend.

EXAMPLE VI

Industrial production of a calcium hydroxide catalyzed resin suitablefor use in binders, particularly in varying combinations with urea.

Charge Ratio: 3.8 Mol Formaldehyde per 1 Mol phenol

Batch Size: 2400 gals.

Ingredients

    ______________________________________                                        Formaldehyde            1804 Imp. Gals.                                       Phenol                   721 Imp. Gals.                                       Beachville chemical .[.hydrate.]..Iadd.hydroxide .Iaddend.-                                            750 lbs.                                             Ca(OH).sub.2 taken as 91.4%                                                   ______________________________________                                    

Procedure

The 3000 gal. reactor was charged with formaldehyde and phenol. Theagitator was started. The catalyst (calcium hydroxide) was added over aperiod of three hours. The temperature was allowed to rise to 84° F.When all the catalyst was loaded, the temperature was allowed to rise to90° F. then 100° F. and then to 110° F. All these steps were carried outwithin one hour. The temperature was held at 110° F. for about 1/2 hour.The temperature was increased to 120° F. in 15 minutes and held at 120°F. for about 15 minutes. The temperature was allowed to increase the130° F. in about 15 minutes, and held at 130° F. for about one hour. Thetemperature was allowed to increae to 140° F. in about 30 minutes. Thetemperature was allowed to rise to 147° F. in about 26 minutes and heldat 147° F. for about 30 minutes to a free formaldehyde content of 10.5%.The mixture was cooled to 76° F. The pH at the end of reaction was 8.45.

The resin was neutralized with carbon dioxide gas to a pH of 7.2, thensampled for tests.

Results

Properties and composition--see Table I, Example VI.

EXAMPLE VII

Laboratory preparations of a Calcium Oxide catalyzed resin of

Charge Ratio: 4 Mol Formaldehyde per 1 Mol Phenol

Ingredients

    ______________________________________                                        Formaldehyde -                                                                            aqueous - 44% solution                                                                         2218.80 gms                                      Phenol -    USP 98%           781.20 gms                                      Calcium Oxide -                                                                           Ashgrove Springfield                                                                            55.7 gms                                                    high calcium pebble                                                           quicklime - CaO 96.3%                                                         ground to (-10) mesh                                                          on U.S. standard                                                  ______________________________________                                    

Procedure

The formaldehyde was poured into the glass reactor. The agitator wasstarted. Phenol was added, followed by calcium oxide. The temperaturewas allowed to rise to 100° F. in a period of 10 minutes and thetemperature was held at this point for 25 minutes. The temperature wasallowed to rise to 110° F. in 30 minutes, and held at this point for 1hour. The temperature was allowed to rise to 120° F. in 30 minutes, andheld these for 1 hour. The temperature was allowed to rise to 130° l F.in 30 minutes, and held for 1 hour. The temperature was allowed to riseto 140° F. in 30 minutes, and held there until a free formaldehyde of10.7%. The mixture was cooled to 75° F. The pH at the end of thereaction was 8.6. The resin was neutralized with carbon dioxide to a pHof about 7.2, then sampled for testing.

Results

Properties and composition--see Table I, Example VII.

LABORATORY STUDIES

The following laboratory studies relate the unexpected practicaldifferences between prior art resins and the resins prepared underconditions of this disclosure to quantitative analytical data.

STUDY I

2700 to 3000 cc of mixtures of U.S.P. phenol (98.0%) and 44.1% aqueousformaldehyde solution (0.3% methanol) were prepared with mol ratiosranging from 1 mol phenol to from 2.8 to 4.4 mols formaldehyde and withan initial water content of from 6.0 mol to 10.0 mol of water per moleof the reactants.

The mixtures were catalyzed with either sodium hydroxide, or barium.Iadd.hydroxide .Iaddend.pentahydrate for comparison with calciumhydroxide as catalyst.

In keeping with past practice for phenol formaldehyde resols for bondingglass fibres, the catalyst concentrations were chosen as follows:

    ______________________________________                                        Sodium Hydroxide (as 50.0% solution)                                          2.5 percent Na on  OR: .1022 mol NaOH                                         the weight of phenol   per mol of phenol                                      Barium Hydroxide (98.5% Pentahydrate)                                         6.5 percent Ba on  OR: .0446 Mol Ba(OH).sub.2                                 the weight of phenol   per mol of phenol                                      Calcium Hydroxide (94.5% Ca(OH).sub.2)                                        3.5 to 6.7 percent Ca on  OR:                                                                        .0822 to .1533 mol                                                            Ca(OH).sub.2 per                                       the weight of phenol   mol of phenol.                                         ______________________________________                                    

(This range closely approximating catalyst solubility in the reactants).

Glass reaction vessels were used throughout.

The following cycle was followed for all laboratory cooks of resins forthis study:

a. Phenol and formaldehyde were blended and brought to a temperature notexceeding 85° F., then held at 85° F.

b. Catalyst was added over 15 minutes, and the cook cycle timed from thefirst catalyst addition.

c. The temperature was allowed to rise in linear fashion 1° F. every 3minutes until it reached 150° F.

d. The temperature was held at 150° F. to the end of the cook cycle,i.e.: to initial loss of dilutability with 19 parts of distilled wateror to constant (lowest) Free Formaldehyde content whichever is reachedfirst.

e. The resol solution was cooled to below 75° F., and divided into twoequal portions.

One portion was left as cooked, the second portion was neutralized, inkeeping with industrial practice:

Sodium resins were neutralized to pH 7.3 with hydrochloric acid (35%).

Barium resins were neutralized to pH 7.3 with dilute sulphuric acid(35%).

Calcium resins were neutralized to pH 7.6 with carbon dioxide gas.

Quantities of each of the non-neutralized and neutralized portions ofeach resin cook were used for evaluation of resin composition andproperties.

The following were observed and recorded, on the samples taken as above,after termination of the cook:

By measurements on resin samples, as produced:

Free (unreacted) formaldehyde

Water dilutability

pH

Free (unreacted) phenol (by gas chromatography

Solids

Ash

Organic Solids

Shelf Life (stability) at:-20° F., 32° F., 75° F., 100° F.,

By gas chromatography on silylized resin samples:

Phenol

.[.o-Monomethylol Phenol.].

.[.p-Monomethylol Phenol.].

.[.Diphenyl with O substitutions.].

.[.o-o Dimethylol Phenol.].

.[.o-p Dimethylol Phenol.].

.[.o-o-p Trimethylol Phenol.].

.[.Diphenyl with 4 substitutions.]..Iadd.

2-Monomethylol Phenol

4-Monomethylol Phenol

2,4-Dimethylol Phenol

2,4-Dimethylol Phenol Monohemiformal

2,4,6-Trimethylol Phenols

Tetra-substituted Diphenyls .Iaddend.Neutralized resin samplescontaining inorganic precipitates (of barium sulphate or calciumcarbonate) were centrifuged prior to gas chromatography.

The results of this study are presented in Table II. Values which aresignificantly different (higher or lower) for calcium catalyzed resinswhen compared to sodium or barium catalyzed resins are underlined foreasier reading. The equilibria between the methylolated phenols, can beeasily disturbed on addition of acids or salts. It is therefore notsurprising that the measurements obtained on the non-neutralized resinsare more consistent throughout the range of mol ratios investigated.Contrary to prior art indications and teachings catalyzation by calciumhydroxide proceeds qualitatively and quantitatively to different resultsthan catalyzation by sodium hydroxide or barium hydroxide. Thedifferences show up increasingly with increasing mol ratios offormaldehyde to phenol. More of the available formaldehyde is convertedinto organic solids and less .[.trimethylol phenol and.]. diphenylcompounds are formed starting at the lowest mol ratio examined. Startingfrom formaldehyde:phenol mol ratio 3.2:1 up, formation of.[.o-o-dimethylol phenol.]. .Iadd.2,4-dimethylol phenol monohemiformal.Iaddend.is minimized. Most strikingly, the formation of.[.o-p-dimethylol phenol.]. .Iadd.2,4,6-trimethylol phenols .Iaddend.isfavoured by the presence of calcium hydroxide .[.is.]. .Iadd.as.Iaddend.catalyst increasingly so for mol ratios 3.5:1 and up.Furthermore, a marked reduction in residual monomethylol phenols isobserved for mol ratios 3.6:1 and up.

STUDY II was undertaken to more clearly separate the effects ofselective catalyzation by calcium hydroxide from those resulting fromhigh catalyst concentrations per se.

The procedures described for Study I were followed throughout except forthe amounts of catalyst added. These were chosen to match exactly thoseused for the calcium catalyzed cooks of Study I.

The soda and barium catalyzed resins were examined for composition andstability only, not for suitability as binder components. Tables III andIV contain the values measured, for three mole ratios of sodiumhydroxide catalyzed resins and two mole ratios of barium hydroxidecatalyzed resins.

The tables compare in each case the resins of this study with those mostclosely corresponding from Study I (=Table II).

Table III indicates clearly that increased levels of sodium hydroxidecatalyst tend to shift values in the direction towards those obtainedwith calcium hydroxide. At no time however are the distinctivedifferences in question in resinification efficiency, i.e.: conversionof more formaldehyde to organic resin solids; cone efficiency; selectiveformation of .[.o p dimethylol phenol.]. .Iadd.2,4,6-trimethylolphenols.Iaddend.; or in reduced formation of diphenyls .[.andtrimethylol phenol.].. Table IV indicates that a formaldehyde:phenol molratio 2.8:1 increased levels of barium hydroxide catalyst minimizedifferences, except resinification efficiency and formation ofdiphenyls. At a mol ratio 3.6:1 they tend to shift values in thedirection towards those obtained with calcium hydroxide.

The distinctive features of the calcium hydroxide catalyzed resin of3.6:1 mole ratio previously discussed herein remain significant, such ashigh resin efficiency; high cone efficiency; reduction in mono-methylolphenol content; preferred formation of .[.o-p-dimethylol phenol.]..Iadd.2,4,6-trimethylol phenols .Iaddend.and reduced formation ofdiphenyls .[.and trimethylol phenol.].. It was reported separately thatpart of the barium .Iadd.hydroxide .Iaddend.catalyst added remainedundissolved, i.e.; exceeded the solubility of barium hydroxide in thesystem, negating the practicality of concentrations approaching orexceeding 0.12 mol of barium hydroxide per mol of phenol.

Summarizing the analytical findings of Studies I, II and III, we haveobserved that within the range of mol ratios of 2.8 to 4.4 molformaldehyde to 1 mol of U.S.P. phenol, and more clearly so from 3.2 to4.4 mol formaldehyde, catalyzation by calcium hydroxide, as compared tosodium hydroxide and barium hydroxide, unexpectedly: favours theformation of .[.ortho-para dimethylol phenol.]. .Iadd.2,4,6-trimethylolphenols.Iaddend.,

reduces the formation of volatile mono methylol phenols,

reduces the formation of the pre-cursors of insoluble higher phenyls,namely .[.o-o-p trimethylol phenol &.]. diphenyls.

We have further observed (probably because of the above selectivecatalyzation) significantly higher resinification and cone efficienciesof the calcium catalyzed resols, as such.

Although not fully understood, it can be further surmised that the verysame compositional differences account for the experience that thecalcium catalyzed resols combine with larger proportions of suchmonomers as urea, melamine or dicyandiamide, or their formaldehydecondensation products, without loss of bond strength.

Table V indicates the hours to complete the reaction and shows calciumto be most economical at all mole rations studied. As the rise intemperature is controlled to be very close for all three catalysts theresult supports the view that the reaction proceeds differently whencalcium hydroxide is the catalyst.

The following Table VI shows comparative stability data for commercialphenol formaldehyde resol solutions kept in storage under industrialconditions. These figures have been prepared by the inventors from dataobserved during long operating experience. Compared are the phenolformaldehyde resol solutions in large scale use for bonding glassfibres:

Sodium Hydroxide catalyzed resins in mole ratios up to 2.5:1

Barium Hydroxide catalyzed resins in mole ratios up to 2.5:1

Calcium Hydroxide catalyzed resins in mole ratios up to 2.8:1 to 3.7:1mol formaldehyde per mol phenol.

The characteristic on which stability is measured for purposes of thistable is the dilutability of the resin solution with distilled water. Itshould be noted that during the period when sodium and barium catalyzedresins were in use, the dilutability was considered acceptable if noless than 800%, indicating that 8 parts of distilled water could beadded to 1 part of resin solution without clouding. On the basis of themore favourable experience with calcium catalyzed resins, the minimumacceptable dilutability has been set at no less than 2000%, and thefigures tabulated indicate in fact a dilutability of over 2400%, i.e.dilution to 25 times the original volume.

Aqueous solutions or dispersions of the special phenol formaledhyderesins disclosed herein are useful for bonding together mineral woolfibres, for instance glass fibres in the formation of fibrous insulationmaterial.

In the manufacture of inorganic fibrous products, phenol formaldehyderesins, or co-condensates of phenol formaldehyde with related resinforming substances have been used as bonding materials for the fibres,in order to impart integrity of shape, dimensions and physicalproperties of the finished product. Such resins are most often used asaqueous solutions or dispersions, rarely alone, most frequently combinedwith other substances, before application to the mineral or glassfibres. The combination of materials is referred to as a "binder".Frequently the other substances are cost reducing extenders, lubricants,dyes or the like.

In other cases, urea, dicyandiamide and/or melamine or their watermiscible condensation products with formaldehyde ("aminoplast resins")are added. These may be intended to reduce exothermic activity typicalof phenolic resins under cure, or they reduce the air pollution whichmay occur on a larger scale during the curing of phenol formaldehyderesins alone. They have a decidedly useful effect upon thetime-temperature-curing speed relationship of the bonding composition,but by themselves exhibit low to poor bond strength, particularly sounder humid conditions.

The phenolic resins and other components are blended in aqueous solutionprior to applying the binder to the glass (or other mineral) fibersbeing formed and collected. Uniformity and stability during prolongedstorage and under exposure to such conditions as agitation, aeration,etc. are important in such binder mixtures.

It has been found unexpectedly that the use of the aqueous selectivelycatalyzed phenol formaldehyde condensates (resols) defined above permitsformulation of binders, which compare most favourably with prior artaqueous binders based upon sodium, barium or calcium catalyzed phenolformaldehyde homo-condensation resins or co-polymer resins of phenolswith other monomers. Given certain minimum target values for thestrength of the bond between the cured resin and the glass fibre, in dryor humid conditions, the novel binder compositions need to contain asmaller proportion of the selectively catalyzed phenolics to amine typemonomer or aminoplast resins. In the examples we show that bindersprepared in accordance with the present procedure show better bondingcharacteristics when containing (along with other conventional binderingredients) 60 parts of the calcium catalyzed phenolic resin to 40parts of urea, or 54 parts of the calcium catalyzed phenolic resin to 46parts of urea, even 50 parts of the calcium catalyzed phenolic resins to50 parts of urea, as compared to binders based upon the prior art bariumand soda catalyzed resins which contain 65-70 parts phenolic resin to35-30 parts of urea.

Good commerical binders have been produced when as little as 30% of thepresent calcium catalyzed phenol formaldehyde resin is combined with 70%of the prior art alkylated amine copolymer resins disclosed for examplein U.S. Pat. No. 3,624,246 issued Nov. 30, 1971, entitled "Water Solubleor Water Dispersible Alkylated Amine Copolymers" of Deuzeman and Lumley;and in U.S. Pat. No. 3,487,048 issued Dec. 30, 1969, entitled"Methylated Melamine-formaldehyde Condensate" of Deuzeman, disclosuresof which are incorporated herein by reference.

Most strikingly, as little as 18 parts of the new resins has beensuccessfully combined with up to 82 parts of a mixture of amine monomerswith amine formaldehyde copolymer resins to produce a useful low-phenolmaterial of good bond strength to glass.

Keeping in mind the exceptionally low content in the phenolic resincomponent itself of volatile phenol and phenol alcohols, there resultbinder compositions which can be applied and cured with greatly reducedemission of air pollutants.

The binder compositions here disclosed are further characterized by avery favourable transition from the water soluble (resol) to theviscous-flowable to the solid (resite) state from the point ofapplication to full cure. This is variably and controllably affectedprimarily by judicious choice of the proportions of phenol formaldehydecondensate to monomeric amines to amine formaldehyde condensatesincorporated into the binder. It can be further affected by the newfreedom to introduce the selective calcia catalyzed resin into thebinder compositions without prior acidic neutralization, because of itssuperior storage stability. The curing characteristics of the bindercompositions particularly those containing from 50-60 parts of phenolformaldehyde resins to 50-40 parts of urea generally parallel those ofthe resin component.

Referring to the commonly accepted A-B-C stages in the cure of aphenolic resin, the phenolic resin exhibits a long A+B stage, good flowcharacteristics in the B stage and a short curing time from B to Cstage. This prevents pre-curing at the point of application (whichadversely affects productivity and quality of the shaped glass fiberarticle), but does not adversely affect the overall speed of cure.Because of this, binder compositions made in accordance with the presentinvention generally may be applied at higher solids concentrations, upto 80%, than the previously known formulations, without incurringpre-cure problems. Thus, the solids level of these binders can be raisedover prior art materials, if desired, with further economic advantage.When prior art materials are used at high solids (exceeding 40%) curingoccurs prematurely and takes place before the resin is fully distributedover the fibres which are to be bonded.

                                      TABLE No. 1                                 __________________________________________________________________________    PROPERTIES AND COMPOSITION OF CALCIUM CATALYSED PHENOLIC                      RESINS MADE IN EXAMPLE I TO VII                                               Example No.       I  II III                                                                              IV V  VI VII                                       __________________________________________________________________________    Mole ratio formaldehyde to phenol                                                               2.8:1                                                                            2.8:1                                                                            3.1:1                                                                            3.5:1                                                                            3.7:1                                                                            3.8:1                                                                            4.0:1                                     Organic solids    48.44                                                                            48.66                                                                            45.61                                                                            42.8                                                                             44.5                                                                             39.63                                                                            40.2                                      Ash as CaO        2.2                                                                              2.2                                                                              2.1                                                                              2.0                                                                              2.03                                                                             1.9                                                                              1.9                                       Free formaldehyde %                                                                             4.5                                                                              4.5                                                                              5.5                                                                              8.6                                                                              8.2                                                                              10.5                                                                             10.7                                      Free phenol, (by gas chromatographic                                                            1.8                                                                              1.8                                                                              0.82                                                                             0.38                                                                             <0.1                                                                             0.14                                                                             0.29                                      analysis)                                                                     pH                8.7                                                                              8.4                                                                              7.9                                                                              8.3                                                                              8.8                                                                              8.45                                                                             8.6                                       *Gel Time (secs)  528                                                                              528                                                                              508                                                                              503                                                                              512                                                                              711                                                                              655                                       Cone Efficiency   -- 73.0                                                                             78.4                                                                             83.4                                                                             -- -- 82.4                                      Dilutability      inf.                                                                             inf.                                                                             inf.                                                                             inf.                                                                             inf.                                                                             inf.                                                                             inf.                                      __________________________________________________________________________     *This test only performed after neutralization of the resin.             

                                      TABLE II                                    __________________________________________________________________________    FINISHED NON-NEUTRALIZED RESINS                                                                                              .[.3.6:3.].                    Mol Ratio      2.8:1       3.2:1   3.4:1   3.5:1                                                                             .Iadd.3.6:1.Iaddend.           __________________________________________________________________________    Formaldehyde to Phenol                                                        Catalyst       Na  Ba  Ca  Na  Ba  Ca  Ca  Ca  Na                             __________________________________________________________________________    By Direct Analysis                                                            Free Phenol    <0.1                                                                              0.1 0.5 0.1 0.7 <0.1                                                                              <0.1                                                                              <0.1                                                                              <0.1                           Free Formaldehyde                                                                            5.2 4.9 4.6 7.5 7.7 6.4 7.4 7.65                                                                              10.18                          Organic Solids 45.9                                                                              46.2                                                                              48.1                                                                              42.7                                                                              43.5                                                                              46.1                                                                              44.8                                                                              44.4                                                                              39.6                           Cone Efficiency                                                                              73.2                                                                              78.7                                                                              77.7                                                                              77.4                                                                              75.6                                                                              79.6                                                                              80.8                                                                              80.9                                                                              79.5                           By Silylization                                                               Phenol         13.6                                                                              15.5                                                                              19.8                                                                              5.7 9.0 11.3                                                                              10.2                                                                              6.3 3.8                            .[.o-methylol.].                                                                             13.8                                                                              10.9                                                                              18.1                                                                              9.4 6.7 11.1                                                                              13.9                                                                              10.0                                                                              7.2                            .Iadd.2-Monomethylol Phenol.Iaddend.                                          .[.p-methylol.].                                                                             11.3                                                                              10.5                                                                              10.6                                                                              7.8 5.9 9.0 10.5                                                                              6.0 7.0                            .Iadd.4-Monomethylol Phenol.Iaddend.                                          .[.Diphenyl (O).].                                                                           17.1                                                                              12.0                                                                              14.3                                                                              14.8                                                                              9.8 12.0                                                                              9.4 12.1                                                                              12.2                           .Iadd.2,4-Dimethylol Phenol.Iaddend.                                          .[.o-o-dimethylol.].                                                                         1.4 0.7 0.5 1.8 1.2 0.7 0.7 0.6 3.4                            .Iadd.2,4-Dimethylol Phenol.Iaddend.                                          .Iadd.Monohemiformal.Iaddend.                                                 .[.o-p-dimethylol.].                                                                         .[.30.7                                                                           34.4                                                                              32.9                                                                              38.3                                                                              42.8                                                                              42.8                                                                              43.3                                                                              50.9                                                                              36.6.].                        .[.o-o-p-trimethylol.].                                                                      .[.4.9                                                                            5.2 2.3 10.3                                                                              13.5                                                                              6.8 7.9 7.4 18.6.].                        .[.Diphenyl (4).].                                                                           .[.7.2                                                                            10.8                                                                              1.5 11.9                                                                              11.1                                                                              6.3 4.1 6.7 11.2.].                        .Iadd.2,4,6-Trimethylol Phenols.Iaddend.                                                     .Iadd.35.6                                                                        39.6                                                                              35.2                                                                              48.6                                                                              56.3                                                                              49.6                                                                              51.2                                                                              58.3                                                                              55.2.Iaddend.                  .Iadd.Tetra-substituted Diphenyls.Iaddend.                                    FINISHED NEUTRALIZED RESINS                                                   By Direct Analysis                                                            Free Phenol    <0.1                                                                              0.4 1.4 0.2 0.85                                                                              <0.1                                                                              <0.1                                                                              <0.1                                                                              <0.1                           Free Formaldehyde                                                                            --  --  --  --  --  --  --  --  --                             Organic Solids 45.3                                                                              44.0                                                                              47.7                                                                              42.4                                                                              42.3                                                                              46.2                                                                              44.7                                                                              44.8                                                                              40.2                           Cone Efficiency                                                                              72.4                                                                              76.1                                                                              75.7                                                                              76.1                                                                              76.9                                                                              77.5                                                                              77.9                                                                              76.4                                                                              78.9                           By Silylization                                                               Phenol         15.4                                                                              21.0                                                                              17.9                                                                              6.8 17.0                                                                              11.9                                                                              9.9 8.4 5.7                            .[.o-methylol.].                                                                             12.3                                                                              12.2                                                                              14.8                                                                              9.4 11.1                                                                              11.3                                                                              13.5                                                                              11.2                                                                              7.1                            .Iadd.2-Monomethylol Phenol.Iaddend.                                          .[.p-methylol.].                                                                             14.8                                                                              11.0                                                                              7.8 7.1 10.1                                                                              9.8 10.5                                                                              8.2 6.6                            .Iadd.4-Monomethylol Phenol.Iaddend.                                          .[.Diphenyl (O).].                                                                           16.9                                                                              11.4                                                                              11.5                                                                              12.2                                                                              12.4                                                                              12.3                                                                              9.2 12.3                                                                              11.9                           .Iadd.2,4-Dimethylol Phenol.Iaddend.                                          .[.o-o-dimethylol.].                                                                         2.6 1.6 1.1 2.6 1.6 0.8 0.8 0.7 4.6                            .Iadd.2,4-Dimethylol Phenol.Iaddend.                                          .Iadd.Monohemiformal.Iaddend.                                                 .[.o-p-dimethylol.].                                                                         .[.28.0                                                                           30.8                                                                              35.1                                                                              39.5                                                                              33.7                                                                              43.2                                                                              41.5                                                                              46.5                                                                              48.4.].                        .[.o-o-p-trimethylol.].                                                                      .[.9.2                                                                            10.2                                                                              10.8                                                                              19.4                                                                              13.1                                                                              9.4 12.0                                                                              11.2                                                                              8.2.].                         .[.Diphenyl (4).].                                                                           .[.0.8                                                                            1.8 1.0 3.0 1.0 1.3 2.6 1.5 7.5.].                         .Iadd.2,4,6-Trimethylol phenols.Iaddend.                                                     .Iadd.37.2                                                                        41.0                                                                              45.9                                                                              58.9                                                                              46.8                                                                              52.6                                                                              53.5                                                                              57.7                                                                              56.6.Iaddend.                  .Iadd.Tetra-substituted Diphenyls.Iaddend.                                    FINISHED NON-NEUTRALIZED RESINS                                               Mol Ratio      3.6:1   3.8:1                                                                             4.0:1       4.4:1                                  __________________________________________________________________________    Formaldehyde to Phenol                                                         Catalyst      Ba  Ca  Ca  Na  Ba  Ca  Na  Ba  Ca                             __________________________________________________________________________    By Direct analysis                                                            Free Phenol    <0.1                                                                              <0.1                                                                              <0.1                                                                              <0.1                                                                              <0.1                                                                              <0.1                                                                              <0.1                                                                              <0.1                                                                              <0.1                           Free Formaldehyde                                                                            10.0                                                                              8.4 9.85                                                                              12.2                                                                              11.9                                                                              10.0                                                                              13.8                                                                              13.8                                                                              12.1                           Organic Solids 41.1                                                                              42.6                                                                              42.6                                                                              37.9                                                                              38.7                                                                              40.9                                                                              36.0                                                                              36.5                                                                              38.1                           Cone Efficiency                                                                              78.5                                                                              83.3                                                                              83.9                                                                              78.2                                                                              74.5                                                                              86.9                                                                              76.6                                                                              76.8                                                                              91.2                           By Silylization                                                               Phenol         7.6 4.1 3.4 2.8 7.5 2.3 2.3 5.9 0.6                            .[.o-methylol.].                                                                             8.2 6.7 5.8 5.6 9.2 5.0 3.8 7.0 1.4                            .Iadd.2-methylol phenol.Iaddend.                                              FINISHED NON-NEUTRALIZED RESINS                                                              .[.2.8:1.]. .[.3.2:1.].                                                                           .[.3.4:1.].                                                                           .[.3.5:1.].                                                                       .[.3.6:3.].                    Mol ratio      .Iadd.3.6:1                                                                          3.8:1                                                                              4.0:1   4.4:1.Iaddend.                             __________________________________________________________________________    .[.p-methylol.].                                                                             9.2 5.5 4.0 6.3 11.8                                                                              4.7 5.7 9.6 1.0                            .Iadd.2-Monomethyl Phenol.Iaddend.                                            .[.Diphenyl (O).].                                                                           11.1                                                                              9.6 9.4 12.3                                                                              10.9                                                                              6.6 11.5                                                                              12.1                                                                              3.4                            .Iadd.2-Dimethylol Phenol.Iaddend.                                            .[.o-o-dimethylol.].                                                                         1.5 1.0 0.7 3.7 1.8 0.4 5.5 2.4 0.6                            .Iadd.2-Dimethylol Phenol.Iaddend.                                            .Iadd.Monohemiformal.Iaddend.                                                 .[.o-p-dimethylol.].                                                                         .[.37.3                                                                           57.6                                                                              54.8                                                                              37.9                                                                              34.8                                                                              58.5                                                                              35.0                                                                              36.8                                                                              58.0.].                        .[.o-o-p-trimethylol.].                                                                      .[.16.8                                                                           9.3 13.7                                                                              20.8                                                                              15.6                                                                              12.8                                                                              24.8                                                                              18.8                                                                              21.0.].                        .[.Diphenyl (4).].                                                                           .[.8.3                                                                            6.2 8.2 10.6                                                                              8.4 9.7 11.4                                                                              7.4 14.0.].                        .Iadd.2,4,6-Trimethylol Phenils.Iaddend.                                                     .Iadd.54.1                                                                        66.9                                                                              68.5                                                                              58.7                                                                              50.4                                                                              71.3                                                                              59.8                                                                              55.6                                                                              79.0.Iaddend.                  .Iadd.Tetra-substituted Diphenyls.Iaddend.                                    FINISHED NEUTRALIZED RESINS                                                   By Direct Analysis                                                            Free Phenol    <0.1                                                                              <0.1                                                                              <0.1                                                                              <0.1                                                                              <0.1                                                                              <0.1                                                                              <0.1                                                                              <0.1                                                                              <0.1                           Free Formaldehyde                                                                            --  --  --  --  --  --  --  --  --                             Organic Solids 40.1                                                                              42.6                                                                              43.4                                                                              37.6                                                                              37.8                                                                              41.5                                                                              36.0                                                                              35.8                                                                              39.2                           Cone Efficiency                                                                              75.9                                                                              78.0                                                                              79.1                                                                              77.0                                                                              73.2                                                                              80.5                                                                              78.4                                                                              76.0                                                                              81.5                           By Silylization                                                               Phenol         9.1 6.3 3.8 3.8 13.0                                                                              1.9 3.2 11.4                                                                              0.6                            .[.o-methylol.].                                                                             7.7 7.9 4.6 5.8 10.3                                                                              4.2 3.4 7.3 1.3                            .Iadd.2-Monomethylol Phenol.Iaddend.                                          .[.p-methylol.].                                                                             8.1 7.0 4.1 6.3 13.2                                                                              4.1 5.9 14.3                                                                              1.3                            .Iadd.4-Monomethylol Phenol.Iaddend.                                          .[.Diphenyl (O).].                                                                           10.3                                                                              12.0                                                                              9.0 11.1                                                                              10.2                                                                              5.8 11.2                                                                              13.2                                                                              4.3                            .Iadd.2,4-Dimethylol Phenol.Iaddend.                                          .[.o-o-dimethylol.].                                                                         1.6 1.0 1.5 4.3 3.0 0.6 4.8 2.7 0.8                            .Iadd.2,4-Dimethylol Phenol.Iaddend.                                          .Iadd.Monohemiformal.Iaddend.                                                 .[.o-p-dimethylol.].                                                                         .[.40.4                                                                           53.3                                                                              51.7                                                                              37.9                                                                              30.0                                                                              52.2                                                                              35.6                                                                              32.7                                                                              58.0.].                        .[.o-o-p-trimethylol.].                                                                      .[.19.7                                                                           11.0                                                                              23.8                                                                              27.5                                                                              19.5                                                                              27.1                                                                              31.5                                                                              17.6                                                                              29.0.].                        Diphenol (4).].                                                                              .[.3.1                                                                            0.6 1.5 3.3 0.8 4.1 4.4 0.8 3.5.].                         2,4,6-Trimethylol Phenol                                                                     .Iadd.60.1                                                                        64.3                                                                              75.5                                                                              65.4                                                                              49.5                                                                              79.3                                                                              67.1                                                                              50.3                                                                              87.0.Iaddend.                  .Iadd.Tetra-substituted Diphenyls.Iaddend.                                    .Iadd.Diphenyls.Iaddend.                                                      __________________________________________________________________________

                                      TABLE III                                   __________________________________________________________________________    Non-Neutralised                                                               Mol Ratio          3.4:1        3.6:1        4.0:1                            __________________________________________________________________________    Formaldehyde to phenol:                                                       Catalyst       NaOH                                                                              NaOH                                                                              Ca(OH).sub.2                                                                       NaOH                                                                              NaOH                                                                              Ca(OH).sub.2                                                                       NaOH                                                                              NaOH                                                                              Ca(OH).sub.2                 Mol % on phenol                                                                              10.22                                                                             11.03                                                                             11.03                                                                              10.22                                                                             11.97                                                                             11.97                                                                              10.22                                                                             13.85                                                                             13.85                        By direct analysis                                                            Free phenol    --  <0.1                                                                              <0.1 <0.1                                                                              <0.1                                                                              <0.1 <0.1                                                                              <0.1                                                                              <0.1                         Free formald.  --  8.55                                                                              7.4  10.2                                                                              9.5 8.4  12.2                                                                              11.6                                                                              10.0                         Organic Solids --  41.8                                                                              44.8 39.6                                                                              40.0                                                                              42.6 37.9                                                                              37.3                                                                              40.9                         Cone Eff.      --  75.6                                                                              80.8 79.5                                                                              79.9                                                                              83.3 78.2                                                                              80.2                                                                              86.9                         By silylisation                                                               Phenol         --  5.4 10.2 3.8 4.4 4.1  2.8 2.0 2.3                          .[.o-methylol.].                                                                             --  7.6 13.9 7.2 6.8 6.7  5.6 3.2 5.0                          .Iadd.2-Monomethylol Phenol.Iaddend.                                          .[.p-methylol.].                                                                             --  9.3 10.5 7.0 8.6 5.5  6.3 4.0 4.7                          .Iadd.4-Monomethylol Phenol.Iaddend.                                           .[.Diphenyl (o).].                                                                          --  195.                                                                              9.4  12.2                                                                              17.8                                                                              9.6  12.3                                                                              13.1                                                                              6.6                          .Iadd.2,4-Dimethylol Phenol.Iaddend.                                          .[.o-o-dimethylol.].                                                                         --  2.2 0.7  3.4 2.1 1.0  3.7 3.8 0.4                          .Iadd.2,4-Dimethylol Phenol.Iaddend.                                          .Iadd.Monohemiformal.Iaddend.                                                 .[.o-p-dimethylol.].                                                                         --  .[.37.3                                                                           43.3 36.6                                                                              39.5                                                                              57.6 37.9                                                                              40.7                                                                              58.5.].                      .[.o-o-p-trimethylol.].                                                                      --  .[.8.8                                                                            7.9  18.6                                                                              10.0                                                                              9.3  20.8                                                                              19.5                                                                              12.8.].                      .[.Diphenyl (4).].                                                                           .[.--                                                                             9.9 6.2  11.2                                                                              10.8                                                                              6.2  10.6                                                                              13.7                                                                              9.7.].                       .Iadd.2,4,6-Trimethyol Phenol.Iaddend.                                                       .Iadd.--                                                                          46.1                                                                              51.2 55.2                                                                              49.5                                                                              66.9 58.7                                                                              60.2                                                                              71.3.Iaddend.                .Iadd.Tetra-substituted Diphenyls.Iaddend.                                    Neutralised                                                                   Mol % on phenol                                                                              10.22                                                                             11.03                                                                             11.03                                                                              10.22                                                                             11.97                                                                             11.97                                                                              10.22                                                                             13.85                                                                             13.85                        By direct analysis                                                            Free phenol    --  <0.1                                                                              <0.1 <0.1                                                                              <0.1                                                                              <0.1 <0.1                                                                              <0.1                                                                              <0.1                         Free formald.  --  --  --   --  --  --   --  --  --                           Organic Solids --  41.4                                                                              46.2 40.2                                                                              40.0                                                                              42.6 37.6                                                                              37.4                                                                              41.5                         Cone Eff.      --  73.6                                                                              77.5 78.9                                                                              76.6                                                                              78.0 77.0                                                                              75.8                                                                              80.5                         By silylisation                                                               Phenol         --  6.2 9.9  5.7 5.2 6.3  3.8 1.7 1.9                          .[.o-methylol.].                                                                             --  7.4 13.5 7.1 5.5 7.9  5.8 1.7 4.2                          .Iadd.2-Monomethylol Phenol.Iaddend.                                          .[.p-methylol.].                                                                             --  9.0 10.5 6.6 7.4 7.9  6.3 2.4 4.1                          .Iadd.4-Monomethylol Phenol.Iaddend.                                          .[.Diphenyl (o).].                                                                           --  15.1                                                                              9.2  11.9                                                                              12.4                                                                              12.0 11.1                                                                              9.5 5.8                          .Iadd.2,4-Dimethylol Phenol.Iaddend.                                          .[.o-o-dimethylol.].                                                                         --  3.7 0.8  4.6 3.7 1.0  4.3 41.3                                                                              0.6                          .Iadd.2,4-Dimethylol Phenol.Iaddend.                                          .Iadd.Monohemiformal.Iaddend.                                                 .[.o-p-dimethylol.].                                                                         --  35.4                                                                              41.5 48.4                                                                              38.0                                                                              53.3 37.9                                                                              41.3                                                                              52.2                         .[.o-o-p-trimethylol.].                                                                      --  18.0                                                                              12.0 8.2 21.2                                                                              11.0 27.5                                                                              31.0                                                                              27.1                         .[.Diphenyl (4).].                                                                           .[.--                                                                             5.2 2.6  7.5 6.6 0.6  3.3 8.0 4.1.].                       .Iadd.2,4,6-Trimethyl Phenyl.Iaddend.                                                        .Iadd.--                                                                          53.4                                                                              53.5 56.6                                                                              59.2                                                                              64.3 65.4                                                                              72.3                                                                              79.3 .Iaddend.               .Iadd.Tetra-substituted Diphenyls.Iaddend.                                    __________________________________________________________________________

                                      TABLE IV                                    __________________________________________________________________________    Non-Neutralised                                                               Mol Ratio                                                                     formaldehyde to phenol                                                                            2.8:1          3.6:1                                      Catalyst       Ba(OH).sub.2                                                                       Ba(OH).sub.2                                                                       Ca(OH).sub.2                                                                       Ba(OH).sub.2                                                                       Ba(OH).sub.2                                                                       Ca(OH).sub.2                          Mol % on phenol                                                                              4.46 8.22 8.22 4.46 11.97                                                                              11.97                                 __________________________________________________________________________    By direct analysis                                                            Free phenol    <0.10                                                                              0.10 0.5  <0.1 <0.1 <0.1                                  Free formald.  4.9  4.3  4.6  10.0 8.6  8.4                                   Organic Solids 46.2 44.8 48.1 41.1 38.2 42.6                                  Cone Eff.      78.7 80.4 77.7 78.5 80.3 83.3                                  By silylisation                                                               Phenol         15.5 15.1 19.8 7.6  7.9  4.1                                   .[.o-Methylol.].                                                                             10.9 12.2 18.1 8.2  8.1  6.7                                   .Iadd.2-Monomethylol Phenol.Iaddend.                                          .[.p-methylol.].                                                                             10.5 15.1 10.6 9.2  8.5  5.5                                   .Iadd.4-Monomethylol Phenol.Iaddend.                                          .[.Diphenyl (o).].                                                                           12.0 13.0 14.3 11.1 12.7 9.6                                   .Iadd.2,4-Dimethylol Phenol.Iaddend.                                          .[.o-o-dimethylol.].                                                                         0.7  0.3  0.5  1.5  0.9  1.0                                   .Iadd.2,4-Dimethylol Phenol.Iaddend.                                          .Iadd.Monohemiformal.Iaddend.                                                 .[.o-p-dimethylol.].                                                                         .[.34.4                                                                            31.6 32.9 37.3 42.9 57.6.].                               .[.o-o-p-trimethylol.].                                                                      .[.5.2                                                                             1.6  2.3  16.8 9.4  9.3.].                                .[.Diphenyl (4).].                                                                           .[.10.8                                                                            11.1 1.5  8.3  9.6  6.2.].                                .Iadd.2,4,6-Trimethyol Phenyols.Iaddend.                                                     .Iadd.39.6                                                                         33.2 35.2 54.1 52.3 66.9.Iaddend.                         .Iadd.Tetra-substituted Diphenyls.Iaddend.                                    Neutralised                                                                   Mol % on phenol                                                                              4.46 8.22 8.22 4.46 11.97                                                                              11.97                                 By direct analysis                                                            Free phenol    <0.1 0.15 1.4  <0.1 <0.1 <0.1                                  Free formald.  --   --   --   --   --   --                                    Organic Solids 44.0 42.0 47.7 40.1 36.6 42.6                                  Cone Eff.      76.1 76.8 75.7 75.9 76.8 78.0                                  By silylisation                                                               Phenol         21.0 20.0 17.9 9.1  7.7  6.3                                   .[.o-methylol.].                                                                             12.2 11.8 14.8 7.7  7.5  7.9                                   .Iadd.2-Monomethylol Phenol.Iaddend.                                          .[.p-methylol.].                                                                             11.0 16.7 7.8  8.1  8.8  7.9                                   .Iadd.4-Monomethylol Phenol.Iaddend.                                          .[.Diphenyl (o).].                                                                           11.4 11.4 11.5 10.3 12.9 12.0                                  .Iadd.2,4-Dimethylol Phenol.Iaddend.                                          .[.o-o-dimethylol.].                                                                         1.6  0.8  1.1  1.6  1.0  1.0                                   .Iadd.2,4-Dimthylol Phenol.Iaddend.                                           .Iadd.Monohemiformal.Iaddend.                                                 .[.o-p-dimethylol.].                                                                         .[.30.8                                                                            32.5 35.1 40.4 45.3 53.3.].                               .[.o-o-p-trimethylol.].                                                                      .[.10.2                                                                            5.8  10.8 19.7 12.2 11.0.].                               .[.Diphenyl (4).].                                                                            .[.1.8                                                                            1.0  3.1  4.6  0.6.].                                     .Iadd.2,4,6-Trimethyol Phenols.Iaddend.                                                      .Iadd.41.0                                                                         38.3 45.9 60.1 57.5 64.3.Iaddend.                         .Iadd.Tetra-substituted Diphenyls.Iaddend.                                    __________________________________________________________________________

                                      TABLE V                                     __________________________________________________________________________                  HOURS TO COMPLETE THE REACTION                                  Mol Ratio                                                                     Formaldehyde to Phenol                                                                     2.8:1                                                                            3.2:1                                                                            3.4:1                                                                            3.5:1                                                                            3.6:1                                                                            3.8:1                                                                            4.0:1                                                                            4.4:1                                       __________________________________________________________________________          Mol per Mol                                                             Catalyst,                                                                           Phenol                                                                  NaOH  .1022  6.5                                                                              6.5                                                                              -- -- 6.5                                                                              -- 6.5                                                                              6.5                                               .1103        5.75                                                             .1197               5.75                                                      .1385                    5.5                                            Ba(OH).sub.2                                                                        .0446  6.5                                                                              6.0                                                                              -- -- 6.0                                                                              -- 5.5                                                                              5.5                                               .0822  4.5                                                                    .1197              3.5                                                  Ca(OH).sub.2                                                                        .0822   4.75                                                                  .1009     5.0                                                                 .1103        4.5                                                              .1150              4.5                                                        .1197               4.75                                                      .1291                 4.5                                                     .1385                     4.75                                                .1573                       4.5                                         __________________________________________________________________________

                                      TABLE VI                                    __________________________________________________________________________    Formaldehyde:                                                                 Phenol Mol Ratio                                                                        Up to 2.5:1  Up to 2.5:1  2.8:1 to 3.7:1                            Catalyst  NaOH         Ba(OH).sub.2 Ca(OH).sub.2                              Resin     As produced                                                                          Neutralized                                                                         As produced                                                                          Neutralized                                                                         As produced                                                                          Neutralized                        __________________________________________________________________________    Storage Temp. °F.                                                      Frozen    --     6 mo. --     6 mo. --     3 yrs.                             30° F.                                                                           Unstable                                                                             2 wks.                                                                              Unstable                                                                             4 wks.                                                                              1 yr.  1 yr.                              50° F.                                                                           "      3-5 days                                                                            "      1 wk. 2 mo.  6 mo.                              70° F.                                                                           "      2 days                                                                              "      4 days                                                                              2 wks. 1 mo.                              __________________________________________________________________________

                  TABLE VII                                                       ______________________________________                                        SHELF LIFE,DAYS                                                               Non-neutralized resin                                                         Resin Mol                                                                             Catalyst       100° F.                                                                             75° F.                             Ratio   Type           Mol/Mol Phenol                                         ______________________________________                                        Formaldehyde to Phenol                                                        2.8:1   NaOH      .1022    16         42                                      3.8:1   "         "        16         72                                      3.6:1   "         "        16         83                                      4.0:1   "         "        16         86                                      4.4:1   "         "        16         >86                                     3.4:1   "         .1103                                                       3.6:1   "         .1197    16         >86                                     4.0:1   "         .1385                                                       2.8:1   Ba(OH).sub.2                                                                            .0446    4          20                                      3.2:1   "         "        8          32                                      3.6:1   "         "        8          36                                      4.0:1   "         "        8          48                                      4.4:1   "         "        8          56                                      2.8:1   "         .0822    8          32                                      3.61    "         .1197    8          36                                      2.8:1   Ca(OH):   .0822    4          24                                      3.2:1   "         .1009    4          24                                      3.4:1   "         .1103    4          24                                      3.5:1   "         .1150    4          >24                                     3.6:1   "         .1197    4          >20                                     3.8:1   "         .1291    4          20                                      4.0:1   "         .1385    4          16                                      4.4:1   "         .1573    4          16                                      ______________________________________                                    

                  TABLE VIII                                                      ______________________________________                                        SHELF LIFE, DAYS                                                              Neutralized                                                                   Formaldehyde                                                                  to Phenol                                                                     Resin Mol     Catalyst                                                        Ratio    Type     Mol/Mol Phenol                                                                             100° F.                                                                        75°  F.                         ______________________________________                                        2.8:1    NaOH     .1022        4      8                                       3.2:1    "        "            4      8                                       3.6:1    "        "            4      12                                      4.0:1    "        "            4      20                                      4.4:1    "        "            4      16                                      3.4:1    "        .1103        4      20                                      3.6:1    "        .1197        4      16                                      4.0:1    "        .1385        4      20                                      2.8:1    Ba(OH).sub.2                                                                           .0446        4      4                                       3.2:1    "        "            4      4                                       3.6:1    "        "            4      8                                       4.0:1    "        "            4      16                                      4.4:1    "        "            4      24                                      2.8:1    "        .0822        4      8                                       3.6:1    "        .1197        4      4                                       2.8:1    Ca(OH).sub.2                                                                           .0822        28     28                                      3.2:1    "        .1009        4      24                                      3.4:1    "        .1103        4      36                                      3.5:1    "        .1150        8      32                                      3.6:1    "        .1197        8      32                                      3.8:1    "        .1291        8      44                                      4.0:1    "        .1385        4      36                                      4.4:1    "        .1573        8      36                                      ______________________________________                                         All resins tested were very stable at 32° F. and -20° F.   

The principal components of the low phenol aqueous thermosettablecompositions suitable for bonding mineral fibre (or paper) productsdisclosed in this application comprise:

a. Aminoplast resins or non-phenolic monomeric materials capable ofco-condensing with formaldehyde.

b. A substantially phenol free infinitely dilutable thermosettablephenol formaldehyde resol solution.

c. Ammonia or a water soluble amine to a pH of about 7 to 9.

d. An acidic curing catalyst in an amount of 0.1 to 2 percent by weightbased on the weight of the resin components.

e. Water to a solids content of 1-80 percent.

The preferred thermosettable binder compositions comprise co-condensiblemonomers chosen from the group consisting of melamine, urea,dicyandiamide, acetone, methanol and glycols and aminoplast resinschosen from urea formaldehyde resin, melamine formaldehyde resin andalkylated amine formaldehyde copolymer resins.

They can be modified further by incorporation of one or more knownbinder additives chosen from the group consisting of coupling agentssuch as silanes, emulsified mineral oil, ammonium lignosulphonate, talloil, finely divided mineral fillers, viscosity control agents, dyes andnon-reactive resins.

An example of an appropriate non-reactive resin would be Vinsol (Trademark of Hercules Chemical Company) which is a dark, brittle, naturalresin derived from naval stores. It has been found very useful as acomponent of the binders for glass insulation fibers, especially wheresuch products are intended for bonding glass fibers for odour freerefrigerator insulation.

The resin component (b) is one of the phenol free aqueous thermosettablephenol formaldehyde condensation resins described earlier in thisapplication as being selectively catalysed from high mol ratio blends ofFormaldehyde to Phenol. The preferred resin is derived from ratio's of3.5 to 3.8 Mols of Formaldehyde to 1 Mol of Phenol. The resin may beintroduced with or without prior neutralization.

The ammonia or water soluble amine (c) is used to adjust the pH of thecomposition, to a preferred value of 8.3-8.6. This may drift on storageto a slightly more acid value. If an amine is used, it may be a volatileamine such as benzylamine, diethylamine, dimethylamine, ehtylamine,methylamine, trimethylamine, monoethanolamine, or a less volatile aminesuch as diethanolamine, triethanolamine or morpholine.

The acid curing catalyst (d) will normally be added in the form of asalt preferably an ammonium or amine salt of conventional acids such assulfuric, phosphoric, sultamic, acetic, maleic and carbonic acids.

The amount of water (e) may be varied over a wide range so as to yieldoptimum application characteristics and will be in the range of 20% andover, most frequently 70% or over.

These binders are further combined, with mineral fibres and especiallyglass fibres to manufacture fibrous insulation products, impartingintegrity of shape and physical properties to the finished product. Theyare particularly applicable to the bonding of batts and other shapedarticles produced from glass fibres, which may be in the form ofcontinuous filaments, chopped fiber or glass wool and the like, formedby a variety of processes such as steam blowing, flame blowing,centrifugal fiberizing and other gaseous entrainment processes.

In one embodiment the present invention provides a shaped articleconsisting of mineral fibers particularly glass fibers bonded with acured bonding agent derived from aqueous binders of this type.

The following examples are intended to exemplify further the principlesof this invention as far as it pertains to the preparation of aqueousheat hardenable binders for glass fibre products and to the productsthere from.

The examples are not intended to be limiting in their scope.

EXAMPLE VIII

The neutralized phenol formaldehyde resins of Examples I thru VII wereused to prepare some typical bonding compositions for glass fibreproducts, in which urea, (solid, or in aqueous 50% solution) wascombined with the phenolic resin. Ammonium Sulphate was used as acidiccatalyst and ammonium hydroxide was used to adjust the pH. Silicone(amino ethyl amino propyl trimethoxysilane) and mineral oil emulsionwere also included in the binders.

The binders were prepared by mixing the ingredients while adding thesein sequence to the phenol formaldehyde resin component.

In large scale operations this mixing procedure can be carried out inbatches or by continuous proportioning pumps. Greater or lesserconcentrations of the basic binder compositions can be prepared byadding less or more water of dilution in a practically desirable rangeof from 1 to 80% organic solids, with the water of dilution added at thetime of preparation, or upon delivery to the point of application of theaqueous bonding composition to the glass fibres.

The compositions and evaluations are shown in Table VII A. It will benoted that the resins of this invention permit the use of significantlylarger proportions of urea then prior resins without loss of excellentbonding properties.

                                      TABLE VII-A                                 __________________________________________________________________________    BINDERS MADE FROM RESINS OR SAMPLES 1-7                                       Calcium catalysed Phenol Formaldehyde Resin                                   Combined with Urea                                                                                                  Pheno-                                                   Wt.                  lic                                                      Ammo-    Wt.         Resin                                                    nium Wt. Sili-                                                                             Wt.     Mole                Gel                    Phenolic      Sulphate                                                                           Ammo-                                                                             cone                                                                              Oil     Ratio                                                                              Binder Standard                                                                              Time                   Resin         10%  nium                                                                              10% mul.    Formal-                                                                            Solids Tensile (Binder             Bin-                                                                             Used  Wt. of                                                                            Wt. of                                                                            Aqueous                                                                            Hy- sol.                                                                              50% Wt. dehyde                                                                             %      Strength                                                                              at                  der                                                                              Table I                                                                             Resin                                                                             Urea                                                                              Sol'n                                                                              droxide                                                                           w.w.                                                                              w.w.                                                                              ater                                                                              to   Phen.                                                                             %  (psi)   2661                Ref.                                                                             References                                                                          (gms)                                                                             (gms)                                                                             (gms)                                                                              (gms)                                                                             (gms)                                                                             (gms)                                                                             (gms)                                                                             Phenol                                                                             Resn.                                                                             Urea                                                                             dry  wet                                                                              secs)               __________________________________________________________________________    8-1                                                                              Example 1                                                                           135 35  10   1   1   20  350 2.8:1                                                                              65  35 717  442                                                                              740                 8-2                                                                              Example 2                                                                           131.5                                                                             40  10   1   1   20  350 3.1:1                                                                              60  40 558  434                                                                              935                 8-3                                                                              Example 3                                                                           126 46  10   1   1   20  350 3.5:1                                                                              54  46 665  453                                                                              1126                8-4                                                                              Example 4                                                                           120 46  10   1   1   10  350 3.6:1                                                                              54  46 852  504                    8-5                                                                              Example 5                                                                           121 46  10   1   1   20  350 3.7:1                                                                              54  46 727  326                                                                              1076                8-6                                                                              Example 6                                                                           126 50  10   1   1   0-20                                                                              350 3.8:1                                                                              50  50 656  457                                                                              1347                8-7                                                                              Example 7                                                                           124 50  10   1   1   20  350 4.0:1                                                                              50  50 403  485                                                                              1437                __________________________________________________________________________

EXAMPLE IX

The calcium catalysed water-soluble resin of Example III (mole ratio 3.1Moles formaldehyde to 1 Mol Phenol was compounded into a binder formineral glass fibres following the general procedure of Example VIII. Analkylated amine co-polymer resin was included as a co-condensing resin.Urea was added as a co-condensing monomer. Ammonium sulphate was addedas an acidic catalyst and ammonium hydroxide was used to adjust the pH.Silicone (amino ethyl .[.amine.]. .Iadd.amino .Iaddend.propyl trimethoxy silane) and mineral oil emulsion were also included in thebinder. The binder was prepared by adding the above in order to thephenolic component. The resin solids of the above had the followingcomposition by weight.

    ______________________________________                                                              %     Parts                                             ______________________________________                                        Calcium catalyzed       18.1    19                                            water-soluble                                                                 phenolic resin                                                                Alkylated amine copolymer                                                                             66.5    70                                            resin                                                                         (UFC-31)                                                                      Urea                    10.5    11                                            Ammonium sulphate       .14                                                   Silicone                .19                                                   Mineral Oil             4.57                                                  TOTAL SOLIDS            100.00  100                                           ______________________________________                                    

The thermosetting alkylated amine-co-polymer was produced by thereaction of melamine, urea, formaldehyde and methanol in the presence ofan alkanol amine and a fatty acid following the art disclosed in U.S.Pat. No. 3,624,245 issued 30 Nov. 1971 intitled "Water Dispersible orWater Soluble Alkylated Amine Copolymers" of Deuzeman et al. At asuitable solids concentration in water, this binder was applied to glasswool which was formed into moulded pipe insulation. A similar insulationmade using barium catalysed phenolic resin mole ratio 2.1 Molsformaldehyde to 1.0 Mol phenol was used as a reference standard forevaluation of the above binder and product. Evaluation of the samples ofmoulded pipe gave the results shown in Table VIIIA. Based on thisevaluation, the experimental material was rated as most suitable formanufacture of moulded pipe insulation.

                                      TABLE VII-A                                 __________________________________________________________________________    MOULDED PIPE TRAIL                                                            TO COMPARE BINDER OF EXAMPLE IX WITH A BINDER MADE FROM                       STANDARD BARIUM CATALYSED RESIN                                                             600° F.                                                                        650° F.                                                                        700° F.                                                                      750° F.                            Properties    Std.                                                                              Expt                                                                              Std.                                                                              Expt.                                                                             Std.                                                                             Expt                                                                             Std Expt                                  __________________________________________________________________________    1     Density(pcf)                                                                          6.7 6.2 6.6 6.2 6.3                                                                              6.1                                                                              6.2 5.9                                   2     Ignition loss %                                                                       7.2 6.8 8.0 7.0 6.7                                                                              6.4                                                                              6.5 6.6                                   3     Extraction Loss                                                               %       5.1 4.7 5.3 4.7 5.2                                                                              4.1                                                                              3.4 3.8                                   4     Durability                                                              a/    Humidity                                                                      Swelling %                                                                            1.5 1.1 0.9 0.8 1.1                                                                              0.7                                                                              1.0 0.5                                         (120° F.) gap                                                          (in)    0.1 0.05                                                                              0.12                                                                              0.05                                                                              0.07                                                                             0.05                                                                             0.09                                                                              0.06                                  b/    Autoclave                                                                     Swelling-%                                                                            7.5 5.7 5.7 2.5 2.2                                                                              1.6                                                                              1.0 0.7                                         (5 psi)                                                                       Gap (in)                                                                              1.05                                                                              0.40                                                                              0.46                                                                              0.14                                                                              0.14                                                                             0.19                                                                             0.10                                                                              0.07                                  5     Punking Spread                                                                (in)    2.82                                                                              2.80                                                                              2.89                                                                              2.89                                                                              2.76                                                                             2.77                                                                             2.95                                                                              2.72                                        (1300° F. probe)                                                       %       101.4                                                                             100.7                                                                             104.0                                                                             104.0                                                                             99.3                                                                             99.6                                                                             106.1                                                                             97.8                                  __________________________________________________________________________

EXAMPLE X

The calcium catalysed water soluble resin of Example VI (3.8 Molsformaldehyde to 1.0 Mol phenol) was compounded into a binder using theingredients and procedure of Example IX so as to yield a product withthe following composition by weight:

    ______________________________________                                                            %      Parts                                              ______________________________________                                        Calcium catalyzed water soluble                                                                     36.0     40                                             phenolic resin                                                                Alkylated amine co-polymer                                                                          31.5     35                                             resin                                                                         Urea                  22.5     25                                             Ammonium sulphate     .45                                                     Silicone              .09                                                     Mineral Oil           9.46                                                                          100.00   100                                            ______________________________________                                    

This binder was used to fabricate a glass fiber refrigeration insulationmaterial of 2 inch nominal thickness, and this product was testedagainst a standard insulation of 3 inch thickness with the followingsatisfactory results.

    ______________________________________                                                           A       B                                                  ______________________________________                                        1.   Recovery (thickness in ins.)                                                                      3.20      2.06                                       2.   Parting strength (lbs/gms)                                                    (a) Machine Direction                                                         (i) as received     0.63      0.83                                            (ii) after autoclaving                                                                            0.31      0.46                                            % loss in strength after                                                      autoclaving         50.8      44.6                                            (b) Cross-machine                                                             (i) as received     0.71      0.82                                            (ii) after autoclaving                                                                            0.37      0.46                                            % loss in strength after                                                      autoclaving         47.9      43.9                                       3.   Density (pcf)       1.13      1.09                                       4.   Compressive Strength at                                                       25% deformation (psi)                                                                             9.2       9.4                                        5.   Ignition loss (%)   5.1       3.8                                                                 5.4       4.2                                        6.   Fiber Index (H.T.)  30.0      30.0                                                                          30.0                                       7.   Extraction loss (%)           11.0                                                                          11.6                                       ______________________________________                                    

EXAMPLE XI

The calcium catalysed water soluble resin of Example VI (1 mole phenolto 3.8 moles formaldehyde) were compounded into a binder using theingredients and procedure of example 8-6 in Table VII A.

This product has the following composition by weight on binder solids:

    ______________________________________                                                            % w.w.  Parts                                             ______________________________________                                        Calcium catalysed water soluble                                               phenol formaldehyde resin                                                                           44.5      50                                            Urea                  44.5      50                                            Ammonium Sulphate     .91                                                     Silicone              0.9                                                     Mineral Oil           10.00                                                                         100.00    100                                           ______________________________________                                    

This binder was used to fabricate a glass fiber refrigeration insulationmaterial of 2 inch nominal thickness, and this product was testedagainst a standard insulation of 3 inch thickness with the followingsatisfactory result.

    ______________________________________                                        Properties of glass fiber refrigeration insulation material                   A - std. nominally 3" thickness material                                      B - experimental insulation made using binder                                 of example XI.                                                                                       A     B                                                ______________________________________                                        1.    Recovery               3.20    2.03                                     2.    Parting strength (lbs./GM)                                                    (a) Machine direction                                                         i/ as received         0.63    0.87                                           ii/ after autoclaving  0.31    0.49                                           % loss in strength after autoclaving                                                                 50.8    43.7                                           (b) Cross-machine                                                             i/ as received                                                                ii/ after autoclaving  0.37    0.45                                           % loss in strength after autoclaving                                                                 47.9    41.6                                     3.    Density (pcf)          1.13    1.15                                     4.    Compressive strength at 25%                                                   deformation (psi)      9.2     10.8                                     5.    ignition loss (%)      5.1     5.6                                                                   5.4     6.1                                      6.    Fiber Index (H.T.)     30.0    30.0                                                                  30.0    30.0                                     7.    Extraction loss (%)    --      9.8                                                                           9.6                                      ______________________________________                                    

A batch of calcium catalysed water soluble resin made as described inExample IV (3.5 Moles formaldehyde to 1.0 mols phenol) was compoundedinto a binder according to the composition and procedure given inexample 8-3 in Table VII A.

The product has the following composition by weight on binder solids:

    ______________________________________                                                              %      Parts                                            ______________________________________                                        Calcium catalyzed water soluble phenol                                        formaldehyde resin      48.5     54                                           Urea                    41.3     46                                           Ammonium sulphate       .91                                                   Silicone                .09                                                   Mineral Oil             9.2                                                                           100.00   100                                          ______________________________________                                    

This binder was applied to glass wool which was shaped into a bondedinsulation board for use as a roof deck material having a thickness ofabout 2 inches.

This roof deck material after curing was evaluated according to thenormal tests for quality and performance, the results of these arerecorded in Table IX. The board was found to be satisfactory.

The standard tests for roof deck material are as follows:

1. Density check (PCF)

2. Compressive strength at 25% deformation (ASTM C-165) (X-head 0.05inch/min.)

a. as received

b. after autoclaving--15 min at 5 psi. All samples indicated normalcompressive properties which coincided accordingly with their respectivedensities.

3. % swelling after autoclaving--15 min 5 psi. All samples were withinthe specification.

4. Ignition loss (%). The samples were all within specification.

5. Extraction loss or degree of cure (%).

6. Fiber diameter (H.T.) hundred thousandths of an inch-organic materialburned off fiber (BOF).

7. Water absorption (%) on ASTM method (Fiberglass Canada Ltd. testmethod No. 9.4).

EXAMPLE XIII

The calcium catalysed water-soluble resin of example V Table I (1 molephenol to 3.7 mole formaldehyde) was compounded into a binder using theingredients and procedure of example 8-5. This binder which has the samecomposition by weight as the binder of Example XII was processed asdescribed in Example XII to produce a roof deck material having athickness of about 2 inches. This roof deck material after curing wasevaluated as described above and found satisfactory. The result of theevaluation is give in Table IX. The results show the roof deck materialof Examples 12 and 13 is very good quality.

                  TABLE IX                                                        ______________________________________                                        EVALUATION OF ROOF DECKING MATERIAL                                           DESCRIBED IN                                                                  EXAMPLES XII AND XIII USING THE TESTS DESCRIBED                               IN EXAMPLE XIII                                                                                    Example   Example                                                             XII       XIII                                                                Binder 8-3                                                                              Binder 8-5a                                                         Resin     Resin                                                               Compos-   Compos-                                                             tion as   tion as                                                             Example   Example                                        Tests                IV        V                                              ______________________________________                                        1.  Density (pcf)        8.8       9.2                                        2.  Compressive strength-deformation                                              at 5% and 25%                                                                 (a) as received 5%   5.8       6.4                                            25%                  19.5      21.3                                           (b) after autoclaving and drying                                              5%                   5.1       6.4                                            25%                  15.2      17.5                                           % loss in strength after autoclaving                                                               22.8      17.8                                       3.  % swelling after autoclaving                                                                       0.63      0.62                                       4.  Ignition loss (%)    11.0      14.3                                       5.  Extraction loss (%)  9.6       7.5                                        6.  Fiber diameter (HT) (BOF)                                                                          62.0      62.5                                       7.  Water absorption (%) 2 tests per                                              board (included membrane)                                                     1.                   3.8       5.5                                            2.                   4.4       5.3                                            Average              4.1       5.4                                        ______________________________________                                    

EXAMPLE XIV

The calcium catalysed water soluble .[.resins.]. .Iadd.resin .Iaddend.ofExample I (mole ratio 1 mole phenol to 2.8 moles formaldehyde) wascompounded into binders using the ingredients and procedures of ExamplesVIII-I. These binders having the following composition by weight on asolids basis.

    ______________________________________                                                            8.1                                                                           wt%    parts                                              ______________________________________                                        Calcium catalysed water soluble                                               phenol formaldehyde   58.5     65                                             Urea                  31.5     35                                             Ammonium sulphate     .91                                                     Mineral Oil           9.0                                                     Silicone              .09                                                                           100.00   100                                            ______________________________________                                    

These binders were processed into a fiberglass board of about 10 lbs.per cubic foot density using standard manufacturing procedures.

The resulting boards were evaluated according to the standard testmethods given and found to be superior when compared to similar boardformed using a conventional sodium catalysed phenol formaldehyde resinmole ratio 2.6 moles formaldehyde to 1 Mole Phenol in an equivalentformulation. The results are shown in Table X.

In Table X are shown physical tests on fiber glass boards, nominaldensity 10 pcf when prepared using binder ref. 8-6 of table VII A, basedon resin of Example VI as compared to a conventional sodium catalysedresin based binder.

A--Fiber glass board made on binder 8-1 from calcium catalysed resinmole ratio 2.8 Moles formaldehyde to 1.0 Mole Phenol

B--Reference std., fiber glass board made on a binder from aconventional sodium catalysed phenolic resin mole 2.6 moles formaldehydeto 1.0 mole phenol.

                  TABLE X                                                         ______________________________________                                        TESTS ON FIBER GLASS BOARDS                                                                        A      B                                                 ______________________________________                                        1.    Density check (pcf)  9.9      8.8                                       2.    Compressive strength at 25%                                                   as rec'd (psi)       24.4     17.7                                            after autoclaving    19.0     13.2                                      3.    % loss in strength after                                                      autoclaving          22.1     25.4                                      4.    % swelling after auto-                                                        claving              0.28     0.70                                      5.    Ignition loss (%)    13.6     10.5                                      6.    Extraction (%)       8.8      8.3                                       7.    Water absorption (%)                                                          2 tests per 12% board                                                         includes membrane 1. 1.1      0.9                                             2                    2.4      1.8                                             AVERAGE              1.8      1.4                                       ______________________________________                                    

EXAMPLE XV

The calcium catalysed water soluble resin of Example II (mole ratio 3.1Moles formaldehyde to 1.0 Mole Phenol) was compounded into the binderswith the following composition on a solids basis using the procedure ofexample .Badd..[.10..]..Baddend. .Iadd.X. .Iaddend.

    ______________________________________                                                            A       B                                                                     wt %    wt %                                              ______________________________________                                        Calcium catalysed water soluble                                               phenol formaldehyde   14.5      48.71                                         Alkylated amine co-polymer                                                    resin (UCF-31)        48.5                                                    Urea                  6.2       25.4                                          Bone Glue             29.61     24.7                                          Ammonium sulphate     .99       .99                                           Silicone              .2        .2                                                                  100.00    100.00                                        ______________________________________                                    

The above binder compositions suitably adjusted with water were used tomanufacture bonded mats of glass wood (tissues) of 10 to 35 mil.thickness. The bone glue component is added as an extender and gellingagent and adhesive.

The mats so prepared were of excellent commercial quality as shown bythe test results recorded in Table XI.

    ______________________________________                                                           Binder A                                                                              Binder B                                           ______________________________________                                        1.    Tensile strength (lbs)(MD)                                                                       36.3      37.3                                             A. As received     36.3      37.3                                             B. After autoclaving                                                                             38.0      31.1                                             C. After aging     40.3      36.9                                       2.    Ignition loss (%)                                                             1.                 25.0      23.0                                             2.                 25.5      22.3                                             AVERAGE            25.3      22.6                                       ______________________________________                                    

EXAMPLE XVI

This is an example of the use in glass fibre bonding compositions of theaqueous phenol formaldehyde resins of this disclosure as produced, i.e.without neutralisation of the catalyst prior to storage. Used wasselectively calcium catalysed phenol formaldehyde resin of a startingmole ratio of 3.7 moles of formaldehyde to 1 Mole Phenol, of the generaltype of Example V, but not neutralized with carbon dioxide from pH 8.55to pH 7.8.

112.4 parts by weight of the above aqueous phenol. formaldehyde solutioncontaining 44.5 weight percent organic solids, or 54 parts of phenolresin solids, were pumped at 50° F. into an agitated vessel and 46 partsby weight of uncoated urea prills were added under agitation until fullydissolved.

This high solids concentrate was combined by means of a set ofproportioning pumps with about 1 part (solids) of Ammonium Sulphate in10% aqueous solution, with 10.0% (solids) of a 50% Mineral Oil emulsionin water, with enough aqueous ammonium to adjust pH from 8.3 to 8.6 andwater to adjust to concentration of this binder composition to from 2 to30% solids.

Where compared to binders containing prior art phenolic resins, and alsowhere compared with the binders as per Example VIII-5 (which containsthe Selectively catalysed phenolic resin in its neutralised form),binders prepared by this method and incorporated industrially into glassfibre products exhibit a marked reduction of emission of phenolicpollutants to atmosphere. They exhibit desirable characteristics in thefinal cure, and increased application efficiencies.

The last mentioned is in agreement with the findings of Study Ipertaining to detrimental effects of neutralisation with acids upon coneefficiencies.

TEST METHODS

All tests were carried following standardized test methods as follows:

Free (unreacted) formaldehyde

50 mls. of a hydroxylamine hydrochloride solution (containing 70 gramsin one liter of distilled water) are placed in a beaker, and the pH isadjusted to 4 with 1.0 N sodium hydroxide solution, while stirring.

Into a second beaker are weighed 6±0.01 grams of the resin sample, 15mls of absolute, formaldehyde free, methanol are added. The content istitrated to pH=4 with 0.5 N sulphuric acid while stirring.

The adjusted hydroxylamine hydrochloride solution is added to the sampleallowed to stand for 5 minutes and the excess titrated back with 1.0 NNaOH to ph=4. The % free formaldehyde=1/2×ml of 1.0 N NaOH used in finaltitration.

Resin Solids

a. Total Solids

Not less than 2 grams of the resin are placed into a weighed ointmenttin, and weighed to 0.001 gram accuracy. Duplicate. To each of the twosamples add 10 ml methyl alcohol and place tins and content in a clusteraround the thermometer in a gravity type constant temperature oven,without lids. Dehydrate the samples for exactly two (2) hours at 300°F.±5%. Replace the lids as soon as possible after opening oven door,cool samples in a dessicator to room temperature and weigh.

Calculate total solids: Final Weight/original×100=% Total Solids

Accept 0.5% difference between dulplicate samples and report as theaverage of the two.

b. Ash Content

Weight 10.0±0.1 grams of resin into a weighed platinum (2.5 in.diameter) evaporating dish with cover. Dehydrate in an oven at 300° F.for one hour, with lid partly open. Transfer into a controlledtemperature muffle furnace at 1000° F. for Na or Ba resins or 1600° F.for Ca resin, ±50° F. Allow the dish to remain in furnace overnight,remove, cool in dessicator and weigh residue. Calculate and report aspercent Na₂ O BaO or: CaO

c. Organic (Resin) solids: Total Solids-ash=organic solids

Cone Efficiency:

This test is carried out following the method and apparatus forevaluating resin or binder systems as described by A. Simison in U.S.Pat. No. 2,653,473. It serves to determine the percentage of resinousproducts retained during the application to mineral fibres, in relationto those introduced into the apparatus under conditions closelysimulating those experienced in manufacture. The balance representsorganics lost by volatilization, which represent potential pollutants.

FREE PHENOL IN PHENOLIC RESIN BY GAS CHROMATOGRAPHY

Suitable diluted samples of phenolic resin are injected into the gaschromatograph and the peak heights compared with those of knownconcentrations of phenol.

Operation Conditions

1. F & M Gas chromatograph model 5750 equipped with 2 SS columns 6 ft.,10% UC-W-98, 80-100 mesh, T.C. detector.

2. Standard phenol solutions in methanol ranging 1% to 8% in sufficientnumber of samples to plot an accurate graph based on the peak height.

    __________________________________________________________________________    Carrier gas                                                                              Helium                                                                              Oven Temp. programmed                                                                      110° C. to 230° C.                Flow rate  30 ml/min.                                                                          Programme rate                                                                             15° C./min.                              Injection Port. Temp.                                                                    350° C.                                                                      Attenuation  512 and 8                                       Detector Temp.                                                                           300° C.                                                     __________________________________________________________________________

Samples are prepared by dilution in methanol to 50% or 25% asconvenient. Any precipitate or other solid matter is allowed to settleor is centrifuged and 4 g. of the clear liquid is injected into the G.C.Standard phenol samples must be run and peak heights measured betweenthe corrected baseline and the peak maxima. ##EQU1##

DETERMINATION OF METHYLOL PHENOLS IN PHENOL-FORMALDEHYDE RESINS BY GASCHROMATOGRAPHY SUMMARY

The methylol phenols constituting a significant portion of the watersoluble phenol formaldehyde resins cannot be determined by direct gaschromatography because they react on heating to temperatures below theirboiling points. It is however possible to replace active hydrogen withTrimethylsilyl groups Si(CH₃)₃. The silylized derivatives are chemicallystable, and do not condense in the injection .[.part.]. .Iadd.port.Iaddend.of a gas chromotagraph, thus permitting separation of the.[.eight.]. .Iadd.seven .Iaddend.silylized derivatives of phenol, themethylol phenols and the diphenyls up to 4 substitutions at temperaturesup to 310° C.

METHOD

A few drops of P/F resin is mixed with an approximate two-fold excess ofBis (Trimethylsilyl) Trifluoro Acetamide and reacted. This usually takesabout 10 mins. helped by slight warming. The resulting product isinjected into the G.C.

Using an F & M model 5750 gas chromatograph with thermal conductivitydetector:

Column--S.S. 6 foot, 3% SE 30 Ultraphase on Chromosorb W highperformance .Badd..[.80. 100.]..Baddend. .Iadd.80-100 .Iaddend.mesh

Carrier Helium--30 ml/min.

Injection Port--300° C.

Detector--300° C.

Programme Temperature--80°-325° C.

Sample size--4 .Iadd.microliters .Iaddend.

Attenuation--256-4

The peak heights of .[.eight.]. .Iadd.seven .Iaddend.silvlized compoundsare measured, totalled and each peak is calculated as a percentage ofthe whole. The .[.eight.]. .Iadd.seven .Iaddend.peaks used for measuringare those which are the most significant in demonstrating essentialdifferences between resins. The figures representing these groupshowever do not present absolute percentages within the total structureof the resin, but show a relationship only.

GEL TIME

A brass cup is provided with a heating device suitable for maintaining aconstant temperature of 130° C.±1° C. The sample is placed in the cupand stirred with a glass stirring rod. As the end-point approaches, testpulls may be made by lifting the rod approx. 2 in. out of the samplewith quick pulls. The end-point is reached when the pulled thread breaksand "snaps back", showing elasticity. The time is noted and recorded inseconds.

IGNITION LOSS

The ignition loss is determined as weight percent of the wool product. Aweighed sample of the material is placed in a muffle oven at 950°F..[.+.]..Iadd.±.Iaddend.25° F. When the organic material has ignitedand the sample is uniform in colour throughout, it is cooled to roomtemperature and weighed and the ignition loss is calculated.

TENSILE STRENGTH

The phenolic resin was combined with urea, ammonium sulphate andsilicone, along with microbeads. The mixture was formed in dogbones,(test bars which are thicker at the ends) and cured. One half of thedogbones are broken dry using a Scott tester and the other half weresubjected to saturated steam under pressure then tested.

COMPRESSION STRENGTH TEST, LIGHT DENSITY GLASS FIBRE PRODUCTS

The resistance to compression of low density insulating material (below6 pounds density in pcf) is determined in pounds/square foot at 25%deformation.

DEFORMATION HARDNESS OF HEAVY DENSITY BOARD (Also weight distribution)

Heavy density glass fibre products (density 8-15 pcf) are testednon-destructively by subjecting to a constant load of 10 psi. Thismethod also provides a means of determining weight distributioncalculated either as lane weights or lane density. The test equipmentemploys a 4 inch diameter pressure foot (12.5 square inches).

AUTOCLAVE SWELLING ROOF INSULATION

Roof insulation is tested to determine the percent of swelling afterexposure for 15 minutes in a steam autoclave capable of maintaining 5psi±1/2 (225°-228° F). An Ames dial gauge is employed to measure thethickness to the nearest 0.001 inch. The pressure foot on the gauge is3/4 inch in diameter.

MOISTURE ABSORPTION, HUMIDITY CABINET

The moisture pick-up by weight or by volume is determined when subjectedto a relative humidity of 95-98% at a temperature of 120° F. for 96hours.

SWELLING OF PIPE INSULATION

The dimensional changes of the pipe insulation is tested by subjectionto high humidity conditions. The humidity cabinet used is capable ofmaintaining a relative humidity of 95%±3% at a temperature of 120° F.±3°F. The samples are measured then left for 96 hours in the humiditycabinet, then wall thickness is remeasured, as is any change incurvature.

WATER ABSORPTION ON GLASS FIBER BASE CAP ROOF INSULATION

This test determines the volume of water that the roof insulation willabsorb when submerged. The maximum water absorption rate shall benominally 3% (max. 12%) by volume in a two hour period as per ASTMG-209.

ANALYSIS FOR DEGREE OF CURE

The percent of uncured binder of the volume products is determined bysolvent extraction in a soxhlet apparatus, using acetone as the solvent.To analyse for oil content, hexane is used as the solvent.

HEAT CONDUCTANCE (K VALUE)

K=rate of heat conductance through a homogeneous material expressed inBTU/sq. ft. hr. °F./in. Also called thermal conductivity.

C VALUE (THERMAL CONDUCTANCE)

C=thermal conductance of a non-homogeneous material or one of anythickness other than 1 inch is defined in BTU/sq. ft. hr. °F. for agiven thickness.

PUNKING TEST

Is the determination of the resistance of the material to smolderingwhen subjected to a very hot probe. It is usually reported in inches,which is the average diameter of the burned out area.

We claim:
 1. A method for making an infinitely dilutable low phenolaqueous solution of thermosettable phenol formaldehyde resin, byselectively catalyzing and controlling the methylolation of phenol withformaldehyde to increase resinification, minimize the content ofmonomethylol phenols and higher phenyls and maximize the content of.[.o-p-dimethylol phenols.]. .Iadd.2,4,6-trimethylol phenols.Iaddend.,thus producing a resin solution component for binder formulations havinglow air and wash water-polluting characteristics when applied to asubstrate, comprising the steps of:a. mixing U.S.P. phenol, in theabsence of other monomers, with aqueous formaldehyde, in an amount of3.5 to 4.5 of moles of formaldehyde per mol of phenol, andcorrespondingly up to about 10 moles of water per mol of the reactants,at a temperature not exceeding about 85° F., and, b. introducing calciumoxide or calcium hydroxide catalyst, with cooling in an amount of 4.9 to7 percent as calcium (Ca) based upon the weight of phenol, (0.11 mol to0.16 mol calcium (Ca) per mol of phenol), c. controlling the exothermicrise in the temperature of the reactants without heat input so as toincrease to not more than about 125° F. during at least the first hourof reaction, d. continuing the methylolation reaction without heat inputat a suitable temperature up to 155° F., and e. terminating saidreaction by cooling when the condensation reaction product issubstantially phenol-free, is still water soluble, and contains between3 to 16% unreacted formaldehyde.
 2. A method as in claim 1 for makinginfinitely dilutable substantially phenol free aqueous solutions ofthermosettable phenol formaldehyde resins, by selectively catalyzing andcontrolling the methylolation of phenol with formaldehyde to increaseresinification, minimize the content of monomethylol phenols and higherphenyls and maximize the content of .[.o-p-dimethylol phenols.]..Iadd.2,4,6-trimethylol phenols.Iaddend., thus producing a resinsolution component for binder formulations having low air and wash waterpolluting characteristics when applied to a substrate, comprising thesteps of:a. mixing U.S.P. phenol, in the absence of other monomers, withaqueous formaldehyde in an amount of 3.5 to 4.4 mols of formaldehyde permol of phenol, and correspondingly from 6 to 10 moles of water per molof the reactants, at a temperature not exceeding about 85° F., and, b.introducing calcium oxide or calcium hydroxide catalyst with cooling upto or near its solubility limit in the aqueous mixture present, catalystin an amount of 4.9 to 7 percent as calcium (Ca) based upon the weightof phenol, 0.11 mol to 0.16 mol calcium (Ca) per mol of phenol), c.controlling the exothermic rise in temperature of the reactants withoutheat input so as to increase to not more than about 125° F. during atleast the first hour of reaction, d. continuing the methylolationreaction without heat input at a suitable temperature up to 155° F., ande. terminating said reaction by cooling when the condensation reactionproduct is substantially phenol free, is still water soluble, andcontains between 3 to 16% unreacted formaldehyde.
 3. A continuous methodas in claim 1 for making infinitely dilutable substantially phenol freeaqueous solutions of thermosettable phenol formaldehyde resins, byselectively catalyzing and controlling the methylolation of phenol withformaldehyde to increase resinification, minimize the content ofmonomethylol phenols and higher phenyls and maximize the content of.[.o-p-dimethylol phenols.]. .Iadd.2,4,6-trimethylol phenols.Iaddend.,thus producing a resin solution component for binder formulations havinglow air and wash water polluting characteristics when applied to asubstrate, comprising the steps of:a. continuously mixing U.S.P. phenol,in the absence of other monomers, with aqueous formaldehyde in an amountof 3.5 to 4.4 moles of formaldehyde per mol of phenol, andcorrespondingly from 6 to 10 moles of water per mol of the reactants,continuously introducing calcium oxide or calcium hydroxide catalystwith cooling up to or near its solubility limit in the aqueous mixturepresent, in an amount of 4.9 to 7 percent as calcium (Ca) based upon theweight of phenol, (0.11 mol to 0.16 mol calcium (Ca) per mol of phenol,while maintaining a temperature of not exceeding about 85° F., b.controlling the exothermic rise in temperature of the reactants withoutheat input so as to increase to not more than about 125° F. during atleast the first hour of reaction, c. continuing the methylolationreaction without heat input at a suitable temperature up 155° F., and d.terminating said reaction by cooling when the condensation reactionproduct is substantially phenol free, is still water soluble, andcontains between 3 to 16% unreacted formaldehyde.
 4. A method as inclaim 1 wherein the formaldehyde is introduced in an amount of 3.5 to 4mols per mol of phenol and the calcium oxide in an amount of from 0.11mol to 0.14 mol calcium per mol of phenol.
 5. A method as in claim 1,wherein the formaldehyde is introduced in an amount of 3.6 to 3.8 molsper mol of phenol, and the calcium oxide or hydroxide in an amount offrom 0.12 mol to 0.13 mol calcium per mol of phenol.
 6. A method as inclaim 1 wherein the reaction is carried out under subatmosphericpressure, and a reflux condenser is employed to maintain the reagentconcentrations.
 7. A method as in claim 1 further comprising the step ofbringing the reaction product to a pH of 7 to 7.6 by addition of anacid.
 8. A method as in claim 7 wherein the acid is chosen fromsulfamic, phosphoric, sulfuric, acetic, maleic and carbonic acids, andtheir ammonium salts.
 9. An aqueous solution of a thermosettable phenolformaldehyde condensation resin made according to the method of claim 1.10. An aqueous solution of a thermosettable phenol formaldehydecondensation resin made according to the method of claim
 7. 11. Inaqueous thermosettable compositions suitable for bonding, comprising amixture of aminoplast resins of nonphenolic monomeric materials capableof co-condensing with formaldehyde, a phenol formaldehyde resin, ammoniaor a water soluble amine, an acidic curing catalyst, and water, theimprovements comprising: the phenol formaldehyde resin is present in theform of an aqueous solution of a thermosettable phenol formaldehydecondensation resin made according to the method of claim 1, the pH ofthe composition is in the range of about 7 to 9, the acidic catalyst ispresent in an amount of 0.1 to 2 percent by weight based on the weightof the resin components, and the water is present to a solids content inthe range of 1-80 percent by weight.
 12. In aqueous thermosettablecompositions suitable for bonding, comprising a mixture of aminoplastresins or nonphenolic monomeric materials capable of co-condensing withformaldehyde, a phenol formaldehyde resin, ammonia or a water solubleamine, an acidic curing catalyst, and water, the improvementscomprising: the phenol formaldehyde resin is present in the form of anaqueous solution of a thermosettable phenol formaldehyde condensationresin made according to the method of claim 6, the pH of the compositionis in the range of about 7 to 9, the acidic catalyst is present in anamount of 0.1 to 2 percent by weight based on the weight of the resincomponents, and the water is present to a solids content of 1-80 percentby weight.
 13. An aqueous bonding composition as in claim 11 where theaminoplast resins are chosen from the group consisting of melamineformaldehyde, urea formaldehyde or alkylated amine formaldehydecopolymer resins, and the co-condensable monomers are chosen from thegroup consisting of urea, dicyandiamide, melamine, methanol and glycols.14. A binder composition as in claim 11 wherein the acidic curingcatalyst is an ammonium salt of an acid selected from the groupconsisting of sulfuric acid, phosphoric acid, sulfamic acid, aceticacid, maleic acid and carbonic acid.
 15. A binder composition as inclaim 11 having a pH in the range of 8.3 to 8.6.
 16. A bindercomposition as in claim 11 wherein the solids content is 2 to 30 percentby weight.
 17. A binder as in claim 11 further comprising one or morebinder components chosen from the group consisting of coupling agents,emulsified mineral oil, ammonium ligno sulfonate, tall oil, finelydivided mineral fillers, animal glue and dyes.
 18. A binder as in claim11 wherein the water soluble amine is chosen from the group consistingof benzylamine, diethylamine, diethanolamine, dimethylamine, ethylamine,methylamine, trimethyl-amine, monoethanolamine, triethanolamine.
 19. Abinder composition as in claim 13 wherein 50 percent by weight of ureasolids are admixed or co-condensed with 50 percent by weight of thephenol formaldehyde resin solids resulting from the selectivecatalyzation by calcium oxide or hydroxide of 3,5 to 4.0 mols offormaldehyde with mol phenol.
 20. A binder composition as in claim 13wherein 46 percent by weight of urea solids are admixed or condensedwith 54 percent by weight of phenol formaldehyde resin solids resultingfrom the selective catalyzation by calcium oxide or hydroxide of 3.5 to3.7 moles of formaldehyde with 1 mole phenol.
 21. A binder compositionas in claim 13 wherein 35 percent by weight of urea solids are admixedor co-condensed with 25 percent by weight of an alkylated aminecopolymer resin solids and with 40 percent by weight of phenolformaldehyde resin solids resulting from the selective catalyzation bycalcium or hydroxide of 3.5 to 3.8 mols of formaldehyde with 1 molphenol.
 22. A binder composition as in claim 13 wherein 5 percent byweight of urea solids are admixed and/or co-condensed with 70 weightpercent of alkylated amine copolymer resin solids and with 25 percent byweight of phenol formaldehyde resin solids resulting from the selectivecatalyzation by calcium oxide or hydroxide of from 3.5 to 3.8 moles offormaldehyde to 1 mol of phenol.